Temperature sensitivity of organic compound destruction in SCWO process

• Published in: Journal of environmental sciences (China) 2014-03, Vol.26 (3), p.512-518
• Main Authors: Tan, Yaqin, Shen, Zhemin, Guo, Weimin, Ouyang, Chuang, Jia, Jinping, Jiang, Weili, Zhou, Haiyun
• Format: Article
• Language: English
• Subjects: density functional theory; molecular descriptors; Organic Chemicals - chemistry; Oxidation-Reduction; supercritical water oxidation; Temperature; Water - chemistry; Water Purification; 分子描述符; 密度泛函理论; 有机化合物; 氧化作用; 氧化过程; 温度敏感性; 超临界水氧化; 量子化学方法
• ISSN: 1001-0742; 1878-7320
• DOI: 10.1016/S1001-0742(13)60454-4

To study the temperature sensitivity of the destruction of organic compounds in supercritical water oxidation process （SCWO）, oxidation effects of twelve chemicals in supercritical water were investigated. The SCWO reaction rates of different compounds improved to varying degrees with the increase of temperature, so the highest slope of the temperature-effect curve （/max） was defined as the maximum ratio of removal ratio to working temperature. It is an important index to stand for the temperature sensitivity effect in SCWO. It was proven that the higher imax is, the more significant the effect of temperature on the SCWO effect is. Since the high-temperature area of SCWO equipment is subject to considerable damage from fatigue, the temperature is of great significance in SCWO equipment operation. Generally, most compounds （/max 〉 0.25） can be completely oxidized when the reactor temperature reaches 500~C. However, some compounds （/max 〉 0.25） need a higher temperature for complete oxidation, up to 560~C. To analyze the correlation coefficients between/max and various molecular descriptors, a quantum chemical method was used in this study. The structures of the twelve organic compounds were optimized by the Density Functional Theory B3LYP/6-311G method, as well as their quantum properties. It was shown that six molecular descriptors were negatively correlated to imax while other three descriptors were positively correlated to imax. Among them, dipole moment had the greatest effect on the oxidation thermodynamics of the twelve organic compounds. Once a correlation between molecular descriptors and imax is established, SCWO can be run at an appropriate temperature according to molecular structure.