Qi Tieyue, Zhang Shuo, Li Tong, Xing Lei, An Shanlong, Li Qiangwei, Wang Lidong
Hebei Key Laboratory of Power Plant Flue Gas Multi-Pollutants Control, Department of Environmental Science and Engineering, North China Electric Power University, Baoding 071003, China.
MOE Key Laboratory of Resources and Environmental Systems Optimization, College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206, China.
Environ Sci Technol. 2023 Oct 17;57(41):15759-15770. doi: 10.1021/acs.est.3c06258. Epub 2023 Sep 25.
Ammonia desulfurization is a typical resource-recovery-type wet desulfurization process that is widely used in coal-fired industrial boilers. However, the sulfur recovery is limited by the low oxidation rate of byproduct (ammonium sulfite), leading to secondary SO pollution due to its easy decomposability. In addition, the high toxic arsenic trace substances coexisting in desulfurization liquids also reduce the quality of the final sulfate product, facing with high environmental toxicity. In this study, nitrogen-doped porous carbon coembedded with lanthanum and cobalt (La-Co@NPC) was fabricated with heterologous catalytic active sites (Co) and adsorption sites (LaOCl) to achieve sulfite oxidation and the efficient removal of high toxic trace arsenic for the recovery of high-value ammonium sulfate from the desulfurization liquid. The La-Co@NPC/S(IV) catalytic system can generate numerous strongly oxidizing free radicals (·SO and ·O) for the sulfite oxidation on the Co site, as well as oxidative detoxification of As(III) into As(V). Subsequently, arsenic can be removed through chemical adsorption on LaOCl adsorption sites. By using the dual-functional La-Co@NPC at a concentration of 0.25 g/L, the rate of ammonium sulfite oxidation reached 0.107 mmol/L·s, the arsenic (1 mg/L) removal efficiency reached 92%, and the maximum adsorption capacity of As reached up to 123 mg/g. This study can give certain guiding significance to the functional material design and the coordinated control of multiple coal-fired pollutants in desulfurization for high-value recovery of sulfur resources.
氨法脱硫是一种典型的资源回收型湿法脱硫工艺,广泛应用于燃煤工业锅炉。然而,硫回收受到副产物(亚硫酸铵)氧化率低的限制,由于其易于分解,导致二次SO污染。此外,脱硫液中共存的高毒性砷痕量物质也降低了最终硫酸盐产品的质量,面临着高环境毒性。在本研究中,制备了负载镧和钴的氮掺杂多孔碳(La-Co@NPC),其具有异质催化活性位点(Co)和吸附位点(LaOCl),以实现亚硫酸盐氧化和高效去除高毒性痕量砷,从而从脱硫液中回收高价值的硫酸铵。La-Co@NPC/S(IV)催化体系可以在Co位点上产生大量强氧化性自由基(·SO和·O)用于亚硫酸盐氧化,以及将As(III)氧化解毒为As(V)。随后,砷可以通过在LaOCl吸附位点上的化学吸附而被去除。使用浓度为0.25 g/L的双功能La-Co@NPC时,亚硫酸铵氧化速率达到0.107 mmol/L·s,砷(1 mg/L)去除效率达到92%,As的最大吸附容量高达123 mg/g。本研究可为功能材料设计以及脱硫过程中多种燃煤污染物的协同控制提供一定的指导意义,以实现硫资源的高价值回收。