富氧燃烧气氛下硫改性废弃物衍生吸附剂脱汞及再生性能

Mercury removal over waste-derived sorbent in oxy-fuel combustion flue gas and its regeneration performance

  • 摘要: 富氧燃烧是一种具有广阔应用前景的碳捕集技术,但是富氧燃烧烟气中的汞会造成铝制CO2压缩设备和换热器脆化腐蚀,存在重大安全隐患。富氧燃烧烟气中汞的脱除仍然面临重大挑战,主要原因在于缺乏经济、高效且具备抗硫抗水性能的吸附剂。前期研究将废旧轮胎与生物质在SO2气氛下共热解,制备了能够高效脱除传统燃煤烟气中汞的废弃物衍生吸附剂,探究了该吸附剂在富氧燃烧烟气中的脱汞行为及反应机理,并评估了吸附剂的循环再生性能。研究结果表明,与空气燃烧烟气相比,吸附剂在富氧燃烧烟气条件下的脱汞性能更加优越,主要归因于CO2促进了吸附剂表面C=O和O—C=O官能团的生成。SO2可与吸附剂表面的硫化物反应生成有机硫等官能团,促进了吸附剂的脱汞过程。NO对吸附剂的脱汞过程具有促进作用,原因是NO在吸附剂表面被氧化为NO2,NO2进一步与汞反应生成Hg(NO3)2。HCl能够促进吸附剂表面C—Cl官能团的生成,增加吸附剂的脱汞活性位点,提升吸附剂的脱汞性能。H2O对吸附剂的脱汞过程仅有轻微抑制作用。吸附剂经过前3次循环再生后,其脱汞性能高于初始状态,但在第4次循环再生后,性能开始下降,低于原始水平,这表明吸附剂的再生使用存在一定的局限性,但在适当条件下仍能保持较好的脱汞效果。

     

    Abstract: Oxy-fuel combustion is a promising carbon capture technology. However, elemental mercury (Hg0) present in oxy-fuel combustion flue gas poses significant safety risks due to its potential to cause embrittlement of aluminum-based CO2 compression equipment and heat exchangers. The challenge of Hg0 removal from oxy-fuel flue gas primarily stems from the lack of cost-effective, efficient sorbents with excellent resistance to SO2 and H2O. Previously, waste-derived sorbents were synthesized through the co-pyrolysis of waste tire and biomass under SO2 atmosphere, which exhibited high performance for Hg0 removal from traditional coal-fired flue gas. The behavior of Hg0 removal over waste-derived sorbents from oxy-fuel combustion flue gas is further explored. The involved Hg0 removal mechanisms and regeneration performance of waste-derived sorbents are also revealed. The results indicate that the sorbents perform better in Hg0 removal under oxy-fuel conditions compared to air combustion. This is mainly because the presence of CO2 promotes the generation of C=O and O—C=O functional groups on the sorbent surface. SO2 promotes Hg0 removal by reacting with surface sulfides to form functional groups (such as sulfur-containing functional groups). NO promotes Hg0 removal by being oxidized into NO2 on the sorbent surface, which further reacts with Hg0 to form Hg(NO3)2. HCl contributes to the formation of C—Cl functional groups on the sorbent surface, increasing the active sites for Hg0 removal. However, H2O slightly inhibits the Hg0 removal process due to competitive adsorption. After three regeneration cycles, the Hg0 removal performance of sorbent surpasses its initial state whereas a decline occurs after the fourth cycle. This indicates that there are some limitations in the regeneration of sorbents, but it still exhibits satisfactory Hg0 removal performance under suitable conditions.

     

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