运输燃料中的含硫化合物依然是空气污染的主要源头.随着人们环保意识日益增强,世界各国对燃料油标准特别是硫含量提出了越来越严格的要求.为了应对燃料油的无硫化趋势,探索新型脱硫技术去除油品中的含硫化合物成为研究热点.吸附脱硫技术(ADS)能够选择性地脱除汽油中的含硫化合物,而不影响其中的烯烃含量,从而避免了加氢精制过程中烯烃饱和导致的辛烷值降低问题,成为目前成熟的清洁油品生产技术.
本文采用微波辅助燃烧技术,将一定化学计量比的金属硝酸盐和尿素混合物快速燃烧反应,成功合成一系列铁氧体吸附剂(MgFe2O4, NiFe2O4, CuZnFe2O4, ZnFe2O4, CoFe2O4).以含有噻吩的正庚烷(总含硫量3000 mg/L)为汽油模型,在固定床反应器中500 oC反应条件下探索了所合成铁氧体吸附剂的吸附脱硫性能.结果表明,铁氧体吸附脱硫活性大小为：MgFe2O4>NiFe2O4>CuZnFe2O4>ZnFe2O4>CoFe2O4.其中MgFe2O4较其他铁氧体具有更高的吸附脱硫性能.这是由于Mg-Fe合金化程度低,而且掺杂的Mg降低了Fe与S之间的相互作用,从而显著提高了吸附脱硫性能.此外, Mg作为一种典型的碱金属可在一定程度上显著促进噻吩分解.
X射线衍射和穆斯堡尔谱作为敏感的结构和组成检测手段,广泛用于解析铁氧体吸附剂在吸附脱硫过程中的结构和相态变化.通过穆斯堡尔谱成功解析了铁氧体中Fe的存在形式及其化合态.对新鲜铁氧体吸附剂、吸附脱硫后的吸附剂以及氧化再生的吸附剂进行监测对比,发现在吸附过程中铁氧体被部分硫化成Fe1-xS和双金属硫化物.在空气中经高温(500 oC)处理可成功实现铁氧体吸附剂再生.本文通过对铁氧体吸附剂的结构解析和性能测试,为新型吸附脱硫剂开发提供了理论依据.
Sulfur in transportation fuels is a major source of air pollution. New strategies for the desulfuriza‐tion of fuels have been explored to meet the urgent need to produce cleaner gasoline. Adsorptive desulfurization (ADS) is one of the most promising complementary and alternative methods. Here‐in, nanocrystalline ferrite adsorbents were synthesized from metal nitrates and urea using a mi‐crowave assisted combustion method. A series of ADS experiments were performed using a fixed‐bed reactor to evaluate the ADS reactivity over the ferrites, which was found to have the order MgFe2O4>NiFe2O4>CuZnFe2O4>ZnFe2O4>CoFe2O4. This effect is explained by the fact that the low degree of alloying of Mg‐Fe and the doped Mg increased the interaction between Fe and S com‐pounds, leading to a significant improvement in the desulfurization capability of the adsorbent. Additionally, Mg can dramatically promote the decomposition of thiophene. X‐ray diffraction and M?ssbauer spectroscopy were used to characterize the fresh, regenerated, and sulfided adsorbents. Although the ferrite adsorbents were partially sulfided to bimetallic sulfides during the adsorption process, they were successfully regenerated after calcining at 500 °C in air.
参考文献
| [1] | Karun Gandotra;B. S. Randhawa.Mossbauer studies of nanosized ferrites preparedby the combustion of metal nitrates—oxalyldihydrazide solutions[J].Hyperfine Interactions: Journal Devoted to Research in the Border Regions of Solid State, Atomic and Nuclear Physics,20081/3(1/3):139-143. |
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