Lin Junhao, Liao Qinxiong, Hu Yaping, Ma Rui, Cui Chongwei, Sun Shichang, Liu Xiangli
School of Environment, Harbin Institute of Technology, Harbin, 150090, China.
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, 518060, China.
J Hazard Mater. 2021 Feb 5;403:123678. doi: 10.1016/j.jhazmat.2020.123678. Epub 2020 Aug 15.
The generation of sulfur-containing pollution products affects the quality of biofuels obtained from the supercritical water gasification (SCWG) of sludge. This study investigates the effects of the gasification temperature, moisture content, and reaction atmosphere on the evolution of sulfur-containing compounds. The results showed that temperature was the key parameter causing the migration of sulfur from sludge to biogas and liquid products. The sludge decomposition reaction was dominated by ionic reactions at 360 °C, while the decomposition of organic matter was converted to free radical reactions as the temperature increased from 380 °C to 440 °C. The mercaptan and thioether contents of the bio-oil decreased to 0.3% at 440 °C. Correspondingly, the concentration of HS increased from 6.7 ppm to 38.0 ppm. The decomposition of organic sulfur with an unstable structure (S-H bond and S-C bond) was the main cause of the increase in the content of HS. Additionally, the solubility and oxidation properties of supercritical water were extremely strong. Some sulfur-containing organic compounds were converted into SO via hydrolysis and oxidation reactions, forming sulfate crystals with heavy metals in the bio-char, which aided in achieving the synergistic immobilization of sulfur and heavy metals.
含硫污染产物的生成会影响通过污泥超临界水气化(SCWG)获得的生物燃料的质量。本研究考察了气化温度、含水量和反应气氛对含硫化合物演变的影响。结果表明,温度是导致硫从污泥迁移至沼气和液体产物的关键参数。在360℃时,污泥分解反应以离子反应为主,而随着温度从380℃升高到440℃,有机物的分解转变为自由基反应。在440℃时,生物油中的硫醇和硫醚含量降至0.3%。相应地,HS的浓度从6.7ppm增加到38.0ppm。结构不稳定的有机硫(S-H键和S-C键)的分解是HS含量增加的主要原因。此外,超临界水的溶解性和氧化性能极强。一些含硫有机化合物通过水解和氧化反应转化为SO,与生物炭中的重金属形成硫酸盐晶体,有助于实现硫和重金属的协同固定。