Oxidation of Polychlorinated Biphenyls (PCBs) in Supercritical Water

超临界水中多氯联苯 (PCB) 的氧化

• 批准号: 0115650
• 负责人: Lawrence Tavlarides
• 金额: $ 22.24万
• 依托单位: Syracuse University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-06-15 至 2005-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0115650&HistoricalAwards=false
• 关键词: Oxidation; Polychlorinated; Biphenyls; PCBs; Supercritical

ABSTRACTPI: Lawrence L. Tavlarides Institution: Syracuse UniversityProposal Number: 0115650The goal of this project is to advance the existing technology of the supercritical water oxidation (SCWO) process by developing fundamental knowledge which can be used to define an efficient and environmentally safe way to destroy toxic polychlorinated biphenyls (PCBs) extracted from contaminated soil/sediments or from disposal sites. PCBs are highly toxic organic pollutants (POPs) included by 122 nations on a recently banned list of chemicals known as the "dirty dozen." The 209 PCB congeners are approximately twice the number of the elements in the Periodic Table and 17 times the number of chlorobenzenes, offering chess0like possibilities of investigations. Systematically selected congeners and the most used industrial PCB mixtures will be oxidized in SCW both neat and methanolic solutions. Emphasis will be on the methanolic solutions due to observed rate-enhancing quality of MeOH on PCB dechlorination. Several solutions obtained by SC-CO2/MeOH extraction from PCB polluted real world sediments will also be studied to couple the extraction and oxidation steps of a soil remediation technology being developed by the PI. This approach will permit one to design and optimally operate competitive SCWO large-scale units for PCBs and other related pollutants under less severe conditions than those proposed without kinetic studies and without reaction rate enhancers. Based on experimental results, reaction kinetics and pathways and structure-reactivity relationships will be developed.PCB oxidation experiments in supercritical water will be conducted in a high-pressure, isothermal plug-flow tubular reactor capable of continuous operation at temperatures up to 873 K and pressures up to 60 MPa. The approach is to select thermodynamic, kinetic and process parameters in order to find the optimum conditions for achieving the strategic goal of safe and efficient PCB destruction under the least aggressive conditions. The main parameters considered are temperature (673 - 874 K), pressure (25 - 35 MPa), residence time (1-240 s), and solute concentration (0.1 - 10 g/L in MeOH, and 10-3 - 10 mmol/L in SCW). This knowledge will be disseminated to the research community through publications and presentations and will provide a model training/education to students, including Native Americans living on PCB contaminated lands.

摘要：劳伦斯·L. Tavlarides研究所：锡拉丘兹大学提案编号：0115650该项目的目标是通过开发基础知识来推进现有的超临界水氧化（SCWO）工艺技术，这些基础知识可用于确定一种有效和环境安全的方法来销毁从受污染的土壤/沉积物或处置场地提取的有毒多氯联苯（PCB）。 多氯联苯是一种剧毒有机污染物（POP），被122个国家列入最近禁止的化学品清单，称为“肮脏的一打”。“209种多氯联苯同源物大约是元素周期表中元素数量的两倍，是氯苯数量的17倍，提供了类似国际象棋的研究可能性。 系统选择的同系物和最常用的工业多氯联苯混合物将在超临界水纯溶液和甲醇溶液中氧化。 重点将放在甲醇溶液上，因为观察到甲醇对多氯联苯脱氯的加速作用。 还将研究从受多氯联苯污染的真实的世界沉积物中通过SC-CO2/MeOH提取获得的几种溶液，以将PI正在开发的土壤修复技术的提取和氧化步骤结合起来。 这种方法将允许一个设计和最佳操作的竞争性SCWO多氯联苯和其他相关污染物的大规模单位在较不严格的条件下比那些没有动力学研究和反应速率增强剂。 根据实验结果，反应动力学和途径和结构反应性relationships将开发。PCB氧化实验在超临界水中将进行在一个高压，等温活塞流管式反应器，能够在温度高达873 K和压力高达60 MPa的连续操作。 所采取的办法是选择热力学、动力学和工艺参数，以便找到最佳条件，实现在侵蚀性最小的条件下安全和有效销毁多氯联苯的战略目标。 考虑的主要参数是温度（673 - 874 K）、压力（25 - 35 MPa）、停留时间（1-240 s）和溶质浓度（在MeOH中为0.1 - 10 g/L，在SCW中为10-3 - 10 mmol/L）。 这一知识将通过出版物和演示文稿传播给研究界，并将为学生提供示范培训/教育，包括生活在多氯联苯污染土地上的美洲原住民。