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首页> 外文会议>3rd International Symposium on Reaction Kinetics and the Development and Operation of Catalytic Processes, Apr 22-25, 2001, Oostende, Belgium >Catalytic Oxidation of Sulfite/Bisulfite in a Falling-Film Absorption Column
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Catalytic Oxidation of Sulfite/Bisulfite in a Falling-Film Absorption Column

机译：落膜吸收塔中亚硫酸盐/亚硫酸氢盐的催化氧化

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摘要

The oxidation of sulfite/bisulfite is a topic, still of interest in wet flue gas desulfurization. The catalytic effect of several transition metals on this reaction is well known, but little data is available about the activity of iron. Target of the present project has been to examine the role of Fe~(2+) and the role of Fe~(2+) combined with Mn~(2+) in sulfite/bisulfite oxidation. The results of the present project indicate, that the role of Fe~(2+) is rather limited to an enhancement of the oxygen mass transfer, while acceleration of the oxidation reaction is based on the catalytic support of Mn~(2+). Catalytic acceleration is based on the activity of Mn~(2+), while Fe~(2+) mainly acts as an oxygen-carrier, which enhances the rate of mass transfer of oxygen. The results of this investigation confirm, that acceleration of the S(Ⅳ) oxidation at pH = 5 will be observed as long as the Fe~(2+)-content is kept below 3- 10~(-3) mol/1. Additional Fe~(2+) will result in a rapid break down of S(Ⅳ)-oxidation. Reason for this break down is the oxidation of Fe~(2+) to Fe~(3+), followed by an immediate formation of Fe(OH)_3 due to the low solubility product of Fe(OH)_3. When increasing the pH-value of the absorption liquor, the concentration limit of Fe~(2+) can be extended to at least twice the value of the limit, observed at pH = 5. The effect is based on a physico-chemical shift of the ratio of bisulfite to sulfite with increasing pH-value, resulting in an increased rate of oxidation of sulfite. As a consequence, oxidation of the oxygen-carrier Fe~(2+) is retarded.
机译：亚硫酸盐/亚硫酸氢盐的氧化是一个主题，在湿法烟道气脱硫中仍然引起人们的兴趣。几种过渡金属对该反应的催化作用是众所周知的，但是关于铁的活性的数据很少。本项目的目标是研究Fe〜（2+）以及Fe〜（2+）与Mn〜（2+）结合在亚硫酸盐/亚硫酸氢盐氧化中的作用。本项目的结果表明，Fe〜（2+）的作用仅限于增强氧的质量转移，而氧化反应的加速则基于Mn〜（2+）的催化载体。催化加速是基于Mn〜（2+）的活性，而Fe〜（2+）主要充当氧气的载体，从而提高了氧气的质量转移率。研究结果证实，只要Fe〜（2+）的含量保持在3〜10〜（-3）mol / 1以下，在pH = 5时，S（Ⅳ）氧化就会加速。额外的Fe〜（2+）会导致S（Ⅳ）-氧化迅速分解。分解的原因是Fe〜（2+）氧化为Fe〜（3+），然后由于Fe（OH）_3的低溶解度产物而立即形成Fe（OH）_3。当增加吸收液的pH值时，Fe〜（2+）的浓度极限可以扩展到至少在pH = 5时观察到的极限值的两倍。其影响是基于物理化学位移pH值越高，亚硫酸氢盐与亚硫酸盐的比例越高，导致亚硫酸盐的氧化速率增加。结果，阻碍了氧载体Fe〜（2+）的氧化。

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