Photocatalytic oxidation of xenobiotics in water with immobilized TIO2 on agitator

Abstract

A novel photocatalytic oxidation reactor, using Degussa P‐25 T_iO₂ 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 T_iO₂ film area and the square root of UV light intensity. These results implied the mineralization efficiency of carbofuran could be improved through increasing T_iO₂ film area and UV light intensity. Accordingly, this novel device showed potential application for degrading xenobiotics in water.     

Degradation of caffeine by conductive diamond electrochemical oxidation

The use of Conductive-Diamond Electrochemical Oxidation (CDEO) and Sonoelectrochemical Oxidation (CDSEO) has been evaluated for the removal of caffeine of wastewater. Effects of initial concentration, current density and supporting electrolyte on the process efficiency are assessed. Results show that caffeine is very efficiently removed with CDEO and that depletion of caffeine has two stages depending on its concentration. At low concentrations, opposite to what it is expected in a mass-transfer controlled process, the efficiency increases with current density very significantly, suggesting a very important role of mediated oxidation processes on the removal of caffeine. In addition, the removal of caffeine is faster than TOC, indicating the formation of reaction intermediates. The number and relative abundance of them depend on the operating conditions and supporting electrolyte used. In chloride media, removal of caffeine is faster and more efficiently, although the occurrence of more intermediates takes place. CDSEO does not increase the efficiency of caffeine removal, but it affects to the formation of intermediates. A detailed characterization of intermediates by liquid chromatography time-of-flight mass spectrometry seems to indicate that the degradation of caffeine by CDEO follows an oxidation pathway similar to mechanism proposed by other advanced oxidation processes.     

活性炭-臭氧体系处理含氰废水的作用机理

针对活性炭催化臭氧化降解低质量浓度含氰废水体系,研究了活性炭吸附、催化作用在催化臭氧化体系中的作用,提出了吸附-催化臭氧化协同作用机理。在活性炭-臭氧体系中,活性炭吸附CN-的能力很弱,活性炭在反应体系中主要起了吸附、催化臭氧的作用。活性炭-臭氧体系降解CN-的过程是臭氧直接氧化、活性炭吸附臭氧与活性炭催化臭氧产生.OH自由基间接氧化三者共同作用的结果。     

亚铁离子生物氧化-还原法连续脱除硫化氢

为了降低工业废气中的硫化氢去除工艺成本和运行费用，对三价铁盐吸收与氧化亚铁硫杆菌对Fe²⁺的生物氧化联合作用脱除H₂S进行了研究。通过生物氧化塔中的固定化氧化亚铁硫杆菌细胞再生的Fe³⁺溶液，在H₂S还原吸收塔中脱除H₂S。通过单因素实验分别优化了生物氧化塔和H₂S吸收塔的运行参数，在生物氧化塔曝气量为150 L/h，停留时间为11 h，吸收液中Fe³⁺浓度为0.121~0.143 mol/L，吸收液流量为0.3 L/h，进气量为100 L/h条件下，进气中H₂S浓度分别为2.28和9.11 mg/L，系统连续运行至200 min时趋于相对稳定，当系统连续运行稳定时，H₂S的脱除率可分别达到95%和91%，脱除效果显著。     

Mn的氧化价态对Mn/γ-Al2O3催化剂催化臭氧氧化气相低浓度甲苯的影响

采用共沉淀法，以Al₂O₃为载体制备Mn/γ-Al₂O₃和Mn-Ce/γ-Al₂O₃催化剂，并分别在N₂气氛和O₂气氛下焙烧。采用固定床连续流动反应器，研究所制备催化剂在室温条件下催化臭氧氧化甲苯的性能。通过XRD、XPS和FTIR等手段对催化剂的结构和组成进行表征。结果表明，Mn/γ-Al₂O₃催化剂具有良好的催化臭氧氧化甲苯和催化臭氧自身分解的性能，共沉淀法制备催化剂的最佳Mn负载量为20%。O₂气氛焙烧和Ce的加入，可以有效提高催化剂的活性和寿命。原因是O₂气氛焙烧和Ce的加入可以提高Mn的氧化价态。催化剂失活的主要原因是有机副产物在催化剂表面吸附堆积，失活催化剂在550℃、空气气氛下焙烧可恢复催化性能。     

Photocatalytic Degradation of the Herbicide Erioglaucine in the Presence of Nanosized Titanium Dioxide: Comparison and Modeling of Reaction Kinetics

The present work mainly deals with photocatalytic degradation of a herbicide, erioglaucine, in water in the presence of TiO₂ nanoparticles (Degussa P-25) under ultraviolet (UV) light illumination (30 W). The degradation rate of erioglaucine was not so high when the photolysis was carried out in the absence of TiO₂ and it was negligible in the absence of UV light. We have studied the influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO₂, irradiation time and initial concentration of erioglaucine on the photodegradation efficiency of erioglaucine. A kinetic model is applied for the photocatalytic oxidation by the UV/TiO₂ system. Experimental results indicated that the photocatalytic degradation process could be explained in terms of the Langmuir–Hinshelwood kinetic model. The values of the adsorption equilibrium constant, K, and the second order kinetic rate constant, k, were 0.116 ppm^{? 1} and 0.984 ppm min^{? 1}, respectively. In this work, we also compared the reactivity between the commercial TiO₂ Degussa P-25 and a rutile TiO₂. The photocatalytic activities of both photocatalysts were tested using the herbicide solution. We have noticed that photodegradation efficiency was different between both of them. The higher photoactivity of Degussa P-25 compared to that of rutile TiO₂ for the photodegradation of erioglaucine may be due to higher hydroxyl content, higher surface area, nano-size and crystallinity of the Degussa P-25. Our results also showed that the UV/TiO₂ process with Degussa P-25 as photocatalyst was appropriate as the effective treatment method for removal of erioglaucine from a real wastewater. The electrical energy consumption per order of magnitude for photocatalytic degradation of erioglaucine was lower with Degussa P-25 than in the presence of rutile TiO₂.     

紫外催化湿式双氧水氧化处理化学镀铜废液

利用化学镀铜废液自身含有的铜作为催化剂，应用紫外催化湿式双氧水氧化工艺处理化学镀铜废液取得了良好效果。通过单因素实验确定的推荐工艺条件为：pH=2.0（保持原始值不变）；不额外投加铜催化剂；H₂O₂用量为2倍理论量。在此条件下处理化学镀铜废液180 min，COD去除率可达到96.6%；之后采用沉淀法回收铜，调节处理后废水pH到9.5，铜的回收率可达到99.8%。     

铁炭-混凝沉淀-生化处理强酸性染料废水的中试研究

采用铁炭-混凝沉淀-水解酸化-生物接触氧化工艺对强酸性染料废水进行中试处理研究。在铁炭微电解单元主要考察了铁炭比、HRT和曝气量大小对处理效果的影响;在水解酸化单元主要考察了进水pH和HRT对处理效果的影响。通过铁炭微电解和水解酸化,在大幅改善废水的可生化性的同时,还可以有效去除废水的色度、削减有机负荷,以保证后续的生物接触氧化工艺的高效稳定运行。在生物接触氧化单元主要考察了进水浓度、HRT对处理效果的影响。经过组合工艺的处理,最终的出水COD〈75 mg/L,出水色度〈40倍。     

不同污泥源条件下ANAMMOX启动及其与反硝化协同脱氮对比

采用城市生活污水配水同时启动两组ASBR,R1接种好氧硝化污泥,R2按2∶1混合接种短程硝化和厌氧氨氧化污泥,研究2个ANAMMOX反应器启动的可行性及其差异。实验结果表明,R1和R2均可成功启动ANAMMOX,R1需130 d,R2仅需73 d;稳定期R1和R2反应器NH4+-N、NO2--N和TN去除率分别达95.30%、91.30%、76.28%和96.2%、98.3%、90.1%,且周期内NH4+-N、NO2--N和NO3--N降解规律相似;R1和R2反应器发生的主要反应为厌氧氨氧化,但同时存在反硝化作用;2组反应器稳定运行后污泥颜色、形态及微生物组成相似,经SEM观察多为球状菌。