Photo-Fenton treatment of water containing natural phenolic pollutants

Phenolic compounds are known to be present in high concentrations in various types of agro-industrial wastes. As they are highly biorecalcitrant, the possibility of treatment by advanced oxidation processes should be investigated. In this work, six model phenolic compounds (vanillin, protocatechuic acid, syringic acid, p-coumaric acid, gallic acid and L-tyrosine) were chosen for a demonstration of degradation by photo-Fenton reaction, under artificial light in laboratory experiments in Vienna and under sunlight in pilot-plant experiments at the Plataforma Solar de Almería in Spain. All compounds were completely mineralised. No non-degradable intermediates were produced, either in experiments with single substances or in a more complex matrix of a mixture of phenolic compounds. The expected selectivity of the photo-Fenton reaction for aromatic compounds was proven by comparison of the decrease in total organic carbon with the removal of total phenolic content.     

水溶液中萘普生的光催化降解及产物的毒性评价

以紫外光为光源,采用photo-Fenton方法降解低浓度的萘普生(NPX)水溶液,确定了最佳降解条件为:pH=3,H2O2质量浓度为500 mg/L,Fe2+质量浓度为15 mg/L.NPX的光催化降解过程符合一级动力学方程.在最佳降解条件下,NPX降解反应速率常数为0.136 0 min-1.NPX溶液对普通小球藻的生长有一定的抑制作用,降解前抑制率为50.54%,降解75min后,抑制率下降至1.99%.photo-Fenton可以降低NPX溶液的生物毒性,适用于处理含低浓度NPX水溶液.     

气相中嗅味物质—壬醛的真空紫外光降解研究

在建立热脱附-气相色谱法分析气相中低浓度壬醛的基础上,研究了不同条件下真空紫外光对气相中低浓度壬醛的光化学降解。结果表明,壬醛的真空紫外光降解率基本不受初始浓度的影响,在所研究的浓度范围(0.13～1.74mg/m3)内符合一级动力学,其表观反应速率常数为2.3 min-1。相对湿度一开始增加时均使得不同浓度的壬醛的去除率降低,但低浓度壬醛的降解随后几乎不再受相对湿度变化的影响,而较高浓度壬醛的去除率则先随相对湿度增加而下降,随后则又上升。壬醛能在极干燥的氮气气氛中被真空紫外光降解,同时它在氮气气氛中的降解率随相对湿度的增加而增加,壬醛在极干燥的氮气、空气和氧气气氛中的降解率依次上升,说明真空紫外光直接光解、光解产生的羟基自由基、光解产生的氧原子或臭氧均能导致壬醛的有效降解,且这3种机制相互影响。     

Photocatalytic degradation of C5–C7 alkanes in the gas–phase

The gas-phase photocatalytic oxidation (PCO) of pentane, i-pentane, hexane, i-hexane and heptane over illuminated titanium at ambient temperatures was studied in a continuous stirring-tank reactor and for different values of VOC feed concentrations and relative humidity levels. Conversions achieved were over 90% for residence times from 50 to 85 s and the only products formed were CO₂ and H₂O, while no catalyst deactivation was observed. The obtained results indicate that the molecular and stereochemical structures of the compounds play an important role in the reaction, as the rate was increasing with higher molecular weight, and the presence of a tertiary carbon atom enhanced the reactivity. It was also observed that the increase of the carbon chain by a methyl group had the same influence in the reaction rate in the case of both pentane and i-pentane, while the ratio of the rates for the linear and branched structure was the same for both C₅ and C₆ isomers. The presence of water in the system had an inhibitory effect in all cases. The PCO kinetics was well fit by a Langmuir–Hinshelwood model, modified so as to take into consideration the influence of water vapour. The rate constants ranged from 1.87 × 10^?7 mol m^?2 s^?1 for pentane to 3.03 × 10^?7 mol m^?2 s^?1 for heptane, and the VOC adsorption constants from 1.14 10⁴ to 2.83 10⁴ m³ mol^?1, while the water adsorption constant was 11.2 m³ mol^?1.     

Synergistic effects of liquid and gas phase discharges using pulsed high voltage for dyes degradation in the presence of oxygen

The technology of combined liquid and gas phase discharges (LGD) using pulsed high voltage for dyes degradation was developed in this study. Apparent synergistic effects for Acid orange II (AO) degradation in the presence of oxygen were observed. The enhancement of AO degradation rate was around 302%. Furthermore, higher energy efficiency was obtained comparing with individual liquid phase discharge (LD) or gas phase discharge process (GD). The AO degradation in the presence of oxygen by LGD proceeded through the direct ozone oxidation and the ozone decomposition induced by LD. Important operating parameters such as electrode distance, applied voltage, pulse repetition rate, and types of dyes were further investigated.     

高级氧化技术降解水中有机磷农药的研究进展

综述了近年来发展迅速的高级氧化技术,主要包括臭氧高级氧化技术、光催化氧化法、超声降解法、电化学水处理技术和超临界水氧化法等.结合有机磷农药废水处理方法的进展,介绍了各种高级氧化技术在机理研究和应用方面取得的成果和存在的问题,并指出了高级氧化技术在有机废水处理方面所具有的潜力.     

Photo-Fenton treatment of TNT contaminated soil extract solutions obtained by soil flushing with cyclodextrin

The technical feasibility and performances of coupling flushing abilities of cyclodextrin solutions for 2,4,6-trinitrotoluene (TNT) removal from contaminated soil and the ability of Photo-Fenton treatment for final disposal of soil extract solutions containing high TNT loads have been investigated at laboratory scale. Methylated-beta-cyclodextrin (MCD) has shown better ability than hydroxypropyl-beta-cyclodextrin (HPCD) to complex TNT. The MCD solution increased the aqueous concentration of TNT in soil extract effluents as much as 2.1 times the concentrations obtained during the water flush of the soil. TNT in soil extract solution has been treated by Photo-Fenton. Our results indicate that MCD has a beneficial effect on the degradation rates of TNT. This relative improvement of TNT degradation rate (1.3 time) in presence of high amounts of hydroxyl radical scavengers can be ascribed to the formation of a ternary complex (TNT-cyclodextrin-iron) which can direct hydroxyl radical reaction toward TNT. Complete mineralization of soil extraction solutions was not achieved and TNT degradation pathway has been elucidated in order to ensure that no potential toxic intermediate is left at the end of the treatment time. After successive TNT hydroxylations, oxidative opening of the TNT aromatic ring quickly occurred, leading to the accumulation of short chain carboxylic acids such as oxalic acid and formic acid.     

Comparison of Fenton and Photo-Fenton Processes for Livestock Wastewater Treatment

In this study, the photochemical degradation of livestock wastewater was carried out by the Fenton and Photo-Fenton processes. The effects of pH, reaction time, the molar ratio of Fe^{2 +}/H₂O₂, and the Fe^{2 +} dose were studied. The optimal conditions for the Fenton and Photo-Fenton processes were found to be at a pH of 4 and 5, an Fe^{2 +} dose of 0.066 M and 0.01 M, a concentration of hydrogen peroxide of 0.2 M and 0.1 M, and a molar ratio (Fe^{2 +}/H₂O₂) of 0.33 and 0.1, respectively. The optimal reaction times in the Fenton and Photo-Fenton processes were 60 min and 80 min, respectively. Under the optimal conditions of the Fenton and Photo-Fenton processes, the chemical oxygen demand (COD), color, and fecal coliform removal efficiencies were approximately 70–79, 70–85 and 96.0–99.4%, respectively.     

凹凸棒石粘土脱硫剂脱除硫化氢实验研究

采用凹凸棒石脱硫剂在常温常压下脱除高浓度硫化氢(H2S),研究了凹凸棒石含量、活性组分含量和焙烧温度等因素在脱除H 2S中对脱硫效率和硫容量的影响.实验结果表明,以凹凸棒石为主原料、添加20%～30%(质量分数)的活性组分后,对高浓度低流速的H2S具有较高的脱除效率和较大的硫容量.     

碳纳米管/二氧化钛/壳聚糖催化薄膜光催化活性及苯降解机理

通过X-射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)和紫外可见光漫反射谱(UV-vis)对碳纳米管/二氧化钛/壳聚糖复合薄膜的晶体结构和形貌进行表征,以室内空气典型污染物气相苯为模型反应物,研究碳纳米管/二氧化钛/壳聚糖催化薄膜的光催化活性及其对苯的光降解机理。结果表明,制备的碳纳米管/二氧化钛/壳聚糖催化薄膜所具有的良好催化活性归功于碳纳米管、二氧化钛和壳聚糖三者的协调效应;气相苯光降解产生的主要中间产物是乙酸乙酯和十一烷,以及少量的丙烯醛、4-羰基-甲基-苯乙酮、十二烷烃、2,4,-二叔丁基苯酚、二十一烷烃。根据红外光谱分析与GC/MS分析结果,进一步提出了气相苯的降解机理过程。     

Study on photocatalytic degradation of gaseous dichloromethane using pure and iron ion-doped TiO2 prepared by the sol-gel method

The synthesis of TiO₂ and Fe–TiO₂ by sol–gel method is demonstrated and characterized. The characterization of TiO₂ and Fe–TiO₂ is performed with instruments, including TGA/DTA, FTIR, UV–Vis, N₂ adsorption and SEM. Dichloromethane is used for the photocatalytic activity test. From the results of dichloromethane photocatalyitc degradation, the calcined temperature of TiO₂ and the presence of water vapor influence the photocatalytic activity. The optimum doping amount of iron ions is 0.005 mol%, and this can enhance the photocatalytic activity, while too great an amount will make the iron ions become recombination centers for the electron–hole pairs and reduce the photocatalytic activity. UV–Vis diffuse reflectance spectra of Fe–TiO₂ show an increase in absorbency in the visible light region with the increase in iron ions doping concentration The intermediate of dichloromethane photodegradation includes CHCl₃, CCl₄, CH₂Cl₂ and COCl₂. The presence of iron ions may reduce the adsorption of Cl element on the surface of the photocatalyst.     

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.     

The application of regenerable sorbents for mercury capture in gas phase

Mercury is a well-known toxic element, and flue gas streams emitted from coal-fired utilities are one of the largest anthropogenic sources of this element. This study briefly reviews the proposed technologies for reducing mercury emissions from coal combustion, focusing on an emerging process which involves the use of regenerable sorbents and especially those loaded with noble metals. Among the mercury species formed during coal combustion, elemental mercury is the most difficult to remove from the flue gases due to its low reactivity and insolubility in water. The widespread interest in using regenerable sorbents with metals is due to their ability to retain elemental mercury. With this technology, not only can efficiencies of 100 % be reached in the retention of elemental mercury but also a way to avoid the generation of new wastes loaded with mercury. This study considers the main aspects that must be taken into account when developing effective regenerable sorbents for mercury capture, with special attention to sorbents containing noble metals. The characteristics of this process are compared with those of other processes in a more advanced state of development.     

利用活性炭纤维有机废气吸附回收装置治理二氯甲烷废气

文章介绍了一种化工生产过程中排出的二氯甲烷废气的治理装置———活性炭纤维有机废气吸附回收装置和治理工艺。由于采用了优越的吸附材料和先进的工艺设计 ,使吸附回收率达 97%以上 ,收到了很好的环境效益和经济效益     

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.     

自制气体扩散电极用于染料废水处理的研究

研究了气体扩散电极用于难降解活性艳红X-3B染料废水的处理,优化了催化剂LaNiO3和气体扩散电极的制备工艺.采用凝胶-溶胶法制备催化剂LaNiO3,其最佳制备工艺为:柠檬酸与金属离子摩尔比1.5:1.0,pH 9,焙烧温度750℃;气体扩散电极的最佳制备工艺为:催化剂用量0.6 g,造孔剂用量0.6 g,聚四氟乙烯(...     

有机物降解产气率模型研究

根据重庆市生活垃圾的组成特点,自配垃圾试样进行有机物降解实验,根据实验期间试样的质量变化,结合降解反应方程式,计算试样的产气量,并建立产气率模型.实验结果表明,试样质量随时间逐渐降低,呈指数型衰减规律.试样在实验初期产气率增加较快,达到产气高峰后逐渐降低.用建立的产气率模型进行计算,计算结果与实测数据比较接近,说明该产...     

Titanium dioxide mediated photocatalytic degradation of monochlorobenzene in aqueous phase

The reaction sequence for the photocatalytic degradation of monochlorobenzene (MCB) in UV/TiO2 process, including substrate adsorption, degradation, and mineralization, was studied. The theoretical maximum quantity of MCB that could be adsorbed onto TiO2 surface in aqueous phase was 0.18+/-0.04 micromol m(-2) of TiO2. In accordance with the upper limit of the relative surface coverage of MCB molecules to surface hydroxyls of TiO2 was around 2.2%, the water molecules as the major adjacent species near TiO2 surface would compete with MCB molecules. Increasing the initial substrate concentration to an appropriate value or enhancing the affinity between the MCB and the TiO2 surface by adjusting the solution pH would promote the photocatalytic degradation. Experimental results revealed that the neutral medium was beneficial for the degradation of MCB. In comparison, the mineralization was most improved at acidic condition. Generally, 90% of the total organic carbon (TOC) was mineralized after 240 min illumination time in the examined pH range except solution pH 11. The suppressed mineralization of MCB at solution pH 11 was ascribed to the lack of adsorption. A simplified 2-step consecutive kinetic model was used to simulate the mineralization.