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In-situ photocatalytic remediation of organic contaminants in groundwater

机译:原位光催化修复地下水中的有机污染物

摘要

This research is about the development of a photocatalytic reactor design, Honeycomb, for in-situ groundwater remediation. Photocatalysis, typically a pseudo first order advanced oxidation process, is initiated via the illumination of UVA light on the catalyst, i.e. titanium dioxide (TiO2). In the presence of oxygen, highly reactive oxidising agents are generated such as superoxide (O2-), hydroxyl (OH·-) radicals, and holes (hvb+) on the catalyst surface which can oxidise a wide range of organic compounds. The target contaminant is methyl tert butyl ether (MTBE), a popular gasoline additive in the past three decades, which gives the water an unpleasant taste and odour at 20 µg L-1, making it undrinkable. This research consists of three major parts, i.e. (i) establishing a suitable catalyst immobilisation procedure, (ii) characterisation and evaluation of reactor models and (iii) scale up studies in a sand tank. TiO2 does not attach well onto many surfaces. Therefore, the first step was to determine a suitable immobilisation procedure by preparing TiO2 films using several potential procedures and testing them under the same conditions, at small scale. The coatings were evaluated in terms of photocatalytic activity and adhesion. The photocatalytic activity of the coatings was tested using methylene blue dye (MB), which is a photocatalytic indicator. A hybrid coating, which comprises a sol gel solution enriched with Aeroxide TiO2 P25 powder, on woven fibreglass exhibited the best adhesion and photocatalytic activity among samples evaluated. Thus, it was used to produce immobilised catalyst for this research. Consequently, the immobilisation procedure was scaled up to synthesize TiO2 coatings for the potential photocatalytic reactor design. The photocatalytic activity of the coatings produced from the scaled up immobilisation procedure were reasonably comparable to that produced at small scale. Due to the UVA irradiation and mass transfer limitations, photocatalytic reactors are typically compact in order to maximise their efficiency to accommodate high flows, particularly in water and wastewater treatment. In the case of groundwater, however, the treatment area can span up to meters in width and depth. Groundwater flow is significantly lower than that of water treatment, as the reactor design does not need to be compact. Considering both factors, a photocatalytic reactor design of hexagonal cross-section (Honeycomb) was proposed, in which the structures can be arranged adjacent to each other forming a honeycomb. A model was constructed and tested in a 4 L column (cylindrical) reactor, using the MB test to characterise the reactor performance and operating conditions. This was followed by a hydraulic performance study, which encompasses single and double pass flow studies. The single pass flow study involves the photocatalytic oxidation (PCO) of MB and MTBE, while the double pass flow study was focused on the PCO of MTBE only. The double pass can simulate two serially connected reactors. Single pass flow studies found that the critical hydraulic residence time (HRT) for the PCO of MB and MTBE is approximately 1 day, achieving up to 84 % MTBE removal. Critical HRT refers to the minimum average duration for a batch of contaminant remaining in the reactor in order to maintain the potential efficiency of the reactor. Double pass studies showed the reactor can achieve up to 95 % MTBE removal in 48 hours, and that reactor performance in the field of serially connected reactors can be estimated by sequential order of single pass removal efficiency. In groundwater, there are likely to be other impurities present and the effects of groundwater constituents on the reactor efficiency were studied. The MTBE PCO rate is affected by the presence of organic compounds and dissolved ions mainly due to the competition for hydroxyl radicals and the deactivation of catalyst surface via adsorption of the more strongly adsorbed organic molecules and ions. Despite the presence of organic compounds and dissolved ions, the reactor achieved about 80 % MTBE removal in 48 hours. A double pass flow study showed that the overall efficiency of the photocatalytic reactor in the field can be estimated via sequential order of its efficiency in a single pass flow study using the actual groundwater sample in the laboratory. A sand tank was designed for the simulation of the clean up of an MTBE plume from a point source leakage using the 200 mm i.d. Honeycomb I prototype. Honeycomb I achieved up to 88.1 % MTBE removal when the contaminated groundwater flowed through (single pass) at 14.6 cm d-1. The critical HRT for Honeycomb I was also approximately 1 day, similar to that in the column reactor. The response of MTBE removal efficiency towards flow obtained in the column reactor and sand tank was generic, indicating that the reactor efficiency can be obtained via testing of the model in the column reactor. The presence of toluene, ethylbenzene and o-xylene (TEo-X) decreased the MTBE removal efficiency in both the sand tank and column reactor. The same set of catalyst and 15 W Philips Cleo UVA fluorescent lamp was operated for a total of about 582 h (24 d) out of the cumulative 1039 h (43 d) sand tank experiments, achieving an overall MTBE removal efficiency of about 76.2 %. The experiments in the column reactor and sand tank exhibited the reliability of the immobilised catalyst produced in this research. This research demonstrates the potential of Honeycomb for in-situ groundwater remediation and also proposes its fabrication and installation options in the field.
机译:这项研究是关于用于原位地下水修复的光催化反应器设计Honeycomb的开发。通过在催化剂即二氧化钛(TiO 2)上UVA光的照射来引发光催化,通常是伪的一级高级氧化过程。在氧气的存在下,会生成高反应性氧化剂,例如超氧化物(O2-),羟基(OH·-)自由基和催化剂表面的空穴(hvb +),它们可以氧化多种有机化合物。目标污染物是甲基叔丁基醚(MTBE),在过去的三十年中它是一种流行的汽油添加剂,在20 µg L-1的条件下,给水带来难闻的味道和气味,使其无法饮用。这项研究由三个主要部分组成,即(i)建立合适的催化剂固定程序,(ii)表征和评估反应堆模型,以及(iii)在沙罐中进行大规模研究。 TiO2不能很好地附着在许多表面上。因此,第一步是通过使用几种可能的方法制备TiO2膜并在相同条件下进行小规模测试来确定合适的固定方法。根据光催化活性和粘附性评估涂层。使用亚甲基蓝染料(MB)(一种光催化指示剂)测试了涂层的光催化活性。在机织玻璃纤维上,包含富含Aeroxide TiO2 P25粉末的溶胶凝胶溶液的混合涂层在所评估的样品中表现出最佳的附着力和光催化活性。因此,它被用于生产用于该研究的固定化催化剂。因此,扩大了固定程序以合成用于潜在的光催化反应器设计的TiO2涂层。由按比例放大的固定程序生产的涂料的光催化活性与小规模生产的涂料相当。由于UVA辐射和传质的限制,光催化反应器通常是紧凑的,以最大化其效率以适应高流量,特别是在水和废水处理中。但是,在地下水的情况下,处理区域的宽度和深度可能长达数米。地下水流量明显低于水处理流量,因为反应堆设计无需紧凑。考虑到这两个因素,提出了六边形横截面(蜂窝状)的光催化反应器设计,其中结构可以彼此相邻排列以形成蜂窝状。使用MB测试表征反应器性能和运行条件,在4 L圆柱(圆柱)反应器中构建模型并进行测试。接下来是水力性能研究,其中包括单程和双程流量研究。单程流动研究涉及MB和MTBE的光催化氧化(PCO),而双程流动研究仅关注MTBE的PCO。双程可以模拟两个串联的反应器。单程流量研究发现,MB和MTBE的PCO的临界水力停留时间(HRT)约为1天,MTBE的去除率最高可达84%。临界HRT是指为了保持反应器的潜在效率而在反应器中保留的一批污染物的最小平均持续时间。双程研究表明,该反应器可在48小时内达到95%的MTBE去除率,而串联连接反应器领域的反应器性能可通过单程去除效率的顺序估算。在地下水中,可能还会存在其他杂质,并研究了地下水成分对反应堆效率的影响。 MTBE PCO速率受有机化合物和溶解离子的存在的影响,这主要归因于对羟基自由基的竞争以及通过吸附度更高的有机分子和离子的吸附而使催化剂表面失活。尽管存在有机化合物和溶解的离子,该反应器在48小时内仍可去除约80%的MTBE。两次通过流量研究表明,在实验室中使用实际地下水样本,通过一次通过流量研究中的光催化反应器效率的顺序可以估算出该领域中光催化反应器的整体效率。设计了一个沙罐,用于模拟使用200 mm内径从点源泄漏处清除MTBE羽流的过程。蜂窝我原型。当受污染的地下水以14.6 cm d-1的流量(单程)通过时,蜂窝I的MTBE去除率高达88.1%。蜂窝I的临界HRT也大约为1天,与柱反应器中的相似。 MTBE去除效率对在塔式反应器和砂池中获得的流量的响应是通用的,这表明可以通过在塔式反应器中测试模型来获得反应器效率。甲苯的存在乙苯和邻二甲苯(TEo-X)降低了砂罐和塔式反应器中MTBE的去除效率。在累积的1039小时(43天)沙池实验中,同一组催化剂和15 W飞利浦Cleo UVA荧光灯共运行了约582小时(24天),实现了约76.2%的总MTBE去除效率。在塔式反应器和砂罐中进行的实验证明了本研究生产的固定化催化剂的可靠性。这项研究证明了蜂窝技术在原位地下水修复中的潜力,并提出了其在现场的制造和安装选择。

著录项

  • 作者

    Lim Leonard Lik Pueh;

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  • 年度 2010
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  • 原文格式 PDF
  • 正文语种 {"code":"en","name":"English","id":9}
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