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基于克勞斯反應的煙氣脫硫離子液體制備硫磺的研究

Study on the efficient production of sulfur from SO2-containing ionic liquid via the liquid-phase Claus reaction

  • 摘要: 有色冶煉煙氣中的二氧化硫(SO2)是一種刺激性的有毒氣體,將其高效的捕獲并轉化成硫磺是行業綠色發展的目標. 離子液體(IL)因穩定性高、可調控性好、可循環性強等特點,在SO2捕獲和資源化回收領域有著巨大的潛力. 本文在離子液體吸收劑介導下,通過耦合克勞斯(Claus)反應,探究了四甲基胍醋酸鹽(TMGAc)體系中SO2的吸收和轉化能力. 實驗結果表明:通過酸堿中和制備的TMGAc離子液體具有優異的SO2吸收能力(吸收溫度為20 ℃,且SO2流速為50 mL·min?1時,每克離子液體能吸收1.06 g SO2),優于相同陽離子吸收劑;在室溫下通入H2S氣體,被捕獲的SO2可以快速原位轉化為硫磺(SO2轉化率高達99%);采用高溫熔化的方式使反應產物固液分離,結合X射線衍射(XRD)、掃描電子顯微鏡(SEM)、X射線能譜(EDS)分析方法,確定了最終產物為S8. 四次循環后,吸收劑的SO2轉化率、質量以及吸收量沒有太大變化. 通過紅外光譜(IR)和核磁共振波譜(NMR)表征方法,提出了TMGAc吸收SO2機理,并研究了吸收劑有水和無水的情況下SO2的轉化機理. 本研究不僅為離子液體高效脫硫提供了基礎,還為SO2資源化再回收提供了思路,助力了有色冶煉行業的綠色高質量發展.

     

    Abstract: Sulfur dioxide (SO2), found in the flue gas of nonferrous smelting, is an irritating and toxic gas that poses significant environmental pollution risks and results in the loss of valuable sulfur resources. China, as a major consumer of sulfur, faces a substantial shortage in domestic supply, relying heavily on imports. Capturing and recovering SO2 in an environmentally friendly and safe way is crucial for the sustainable development of the industry. Ionic liquids (ILs) hold great promise for SO2 capture and resource recovery owing to their unique chemical structures and physical properties, high stability, good controllability and strong recyclability. They offer innovative solutions for addressing air pollution and resource recycling and are expected to have widespread industrial applications, contributing significantly to environmental protection and sustainable resource utilization. Current research on ionic liquid desulfurization mainly focuses on the synthesis of new ionic liquids, their performance in SO2 removal, and recyclability, with less emphasis on the recycling of captured SO2. This study explores the SO2 absorption and conversion efficiency of the tetramethylguanidine acetate (TMGAc) system by coupling the Claus reaction mediated by the ionic liquid absorber. Experimental results indicate that TMGAc, prepared by acid-base neutralization, exhibits excellent SO2 absorption capacity with a saturation adsorption capacity of 1.06 g at 20 ℃ and a SO2 flow rate of 50 mL·min?1, outperforming other absorbers with the same cation. By adding H2S gas, the trapped SO2 can be rapidly converted into sulfur at room temperature, achieving up to 99% conversion. The products from the Claus reaction were heated to sulfur’s melting point, causing the sulfur to liquefy and aggregate, allowing it to separate from the absorbent. The sulfur products were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray energy dispersive spectroscopy (EDS). These results indicated that the prepared sulfur product was S8, demonstrating that the TMGAc ionic liquid, based on the Claus reaction, successfully produced sulfur. After four cycles, the TMGAc absorbent maintained a consistent SO2 conversion rate, absorbent mass, and SO2 absorption capacity, indicating its stability and effectiveness. The absorbent exhibited excellent thermal stability and regenerability during the cycling process, indicating its capacity to be regenerated through the Claus reaction and reused as a recyclable absorbent for SO2 capture. Using infrared spectroscopy (IR) and nuclear magnetic resonance spectroscopy (NMR) characterization methods, the mechanism of SO2 absorption by TMGAc was studied. The results indicate that the interaction among the amino groups on the cation of the absorbent and the hydrogen bonds on the anion is crucial for SO2 capture. Finally, the transformation mechanism of SO2 absorption was explored in aqueous and nonaqueous systems. This study not only provides the foundations for efficient ionic liquid desulfurization of ionic liquids but also explores the potential for SO2 recycling, supporting sustainable and high-quality development in the nonferrous smelting industry.

     

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