Manovic Vasilije, Anthony Edward J
CANMET Energy Technology Centre-Ottawa, Natural Resources Canada, 1 Haanel Drive, Ottawa, Ontario, Canada K1A 1M1.
Environ Sci Technol. 2007 Jun 15;41(12):4435-40. doi: 10.1021/es0629458.
This paper examines the reactivation of spent sorbent, produced from multiple CO2 capture cycles, for use in SO2 capture. CaO-based sorbent samples were obtained from Kelly Rock limestone using three particle size ranges, each containing different impurities levels. Using a thermogravimetric analyzer (TGA), the sulfation behavior of partially sulfated and unsulfated samples obtained after multiple calcination-carbonation cycles in a tube furnace (TF), following steam reactivation in a pressurized reactor, is examined. In addition, samples calcined/sintered under different conditions after hydration are also examined. The results show that suitably treated spent sorbent has better sulfation characteristics than that of the original sorbent. Thus for example, after 2 h sulfation, > 80% of the CaO was sulfated. In addition, the sorbent showed significant activity even after 4 h when > 95% CaO was sulfated. The results were confirmed by X-ray diffraction (XRD) analysis, which showed that, by the end of the sulfation process, samples contained CaSO4 with only traces of unreacted CaO. The superior behavior of spent reactivated sorbent appears to be due to swelling of the sorbent particles during steam hydration. This enables the development of a more suitable pore surface area and pore volume distribution for sulfation, and this has been confirmed by N2 adsorption-desorption isotherms and the Barrett-Joyner-Halenda (BJH) method. The surface area morphology of sorbent after reactivation was examined by scanning electron microscopy (SEM). Ca(OH)2 crystals were seen, which displayed their regular shape, and their elemental composition was confirmed by energy-dispersive X-ray (EDX) analysis. The improved characteristics of spent reactivated sorbent in comparison to the original and to the sorbent calcined under different conditions and hydrated indicate the beneficial effect of CO2 cycles on sorbent reactivation and subsequent sulfation. These results allow us to propose a new process for the use of CaO-based sorbent in fluidized bed combustion (FBC) systems, which incorporates CO2 capture, sorbent reactivation, and SO2 retention.
本文研究了多个二氧化碳捕集循环产生的废吸附剂用于二氧化硫捕集的再活化情况。基于氧化钙的吸附剂样品取自凯利岩石灰石,采用了三个粒径范围,每个粒径范围含有不同的杂质水平。使用热重分析仪(TGA),研究了在管式炉(TF)中经过多次煅烧-碳酸化循环后获得的部分硫酸化和未硫酸化样品在加压反应器中蒸汽再活化后的硫化行为。此外,还研究了水化后在不同条件下煅烧/烧结的样品。结果表明,经过适当处理的废吸附剂比原始吸附剂具有更好的硫化特性。例如,硫化2小时后,超过80%的氧化钙被硫化。此外,即使在4小时后,当超过95%的氧化钙被硫化时,吸附剂仍表现出显著的活性。X射线衍射(XRD)分析证实了该结果,该分析表明,在硫化过程结束时,样品中含有硫酸钙,仅含有微量未反应的氧化钙。废再活化吸附剂的优异性能似乎归因于蒸汽水化过程中吸附剂颗粒的膨胀。这使得能够开发出更适合硫化的孔表面积和孔体积分布,这已通过氮气吸附-脱附等温线和巴雷特-乔伊纳-哈伦达(BJH)方法得到证实。通过扫描电子显微镜(SEM)检查了再活化后吸附剂的表面积形态。观察到氢氧化钙晶体,其呈现出规则形状,并通过能量色散X射线(EDX)分析确认了其元素组成。与原始吸附剂以及在不同条件下煅烧和水化的吸附剂相比,废再活化吸附剂的改进特性表明了二氧化碳循环对吸附剂再活化和后续硫化的有益作用。这些结果使我们能够提出一种在流化床燃烧(FBC)系统中使用基于氧化钙的吸附剂的新工艺,该工艺包括二氧化碳捕集、吸附剂再活化和二氧化硫保留。