高硫石油焦中低温（900℃以下）气相催化脱硫方法及其机理研究

A middle-low temperature (<900℃)gas-phase catalytic desulfurization method for high-sulfur petroleum coke is presented in this project, since the increasing sulfur content of petroleum coke has seriously affected the normal production of aluminum electrolysis industry. It introduces a sort of non-oxidation gas into coke calcination process to go through the opening hole of coke and react with sulfur-containing group in the interior of petroleum coke particles, therefore lowering the activation energy of sulfur breaking from carbon skeleton and achieving the desulfurization reaction below 900℃.This project will, by analyzing the characteristics of the gas catalyst proven to work in our past work and its reaction features,and comparing the comprehensive desulfurization effects of some gases with the similar characteristics, confirm the most optimal gas catalyst; by using a variety of modern physical and chemical detection methods, study the reaction mechanism and kinetics of middle-low temperature gas-phase catalystic desulfurization reaction,reveal the thermal structural transformation characteristics of sulfur-containing group and the mass transfer behavior of organic sulfur during the reaction process, eventually achieve the optimization of desulfurization reaction conditions; base on above research, develop an technology prototype combining middle-low temperature gas-phase catalystic desulfurization method and conventional petroleum coke high temperature (1200-1350℃) calcination process.The project results will lay the theoretical foundation for the development of an energy conservation and environment protection atmosphere calcining desulfurization technology.

石油焦中硫含量的增加已严重影响到铝电解工业的正常生产，项目提出了一种高硫焦中低温（<900℃）气相催化脱硫方法，通过在高硫焦煅烧时引入某种非氧化性气相介质，使其经由焦的孔洞结构直接与焦内部的含硫基团发生作用，降低硫从碳骨架上脱除所需的活化能，达到在中低温下脱除高硫焦中有机硫的目的。项目将对已发现的有效气相催化介质特性及其脱硫反应特征进行研究，通过比较相似特质的气体介质的综合脱硫效果，确定最优气相催化介质；利用各种现代物理化学检测和表征手段，研究高硫焦中低温气相催化脱硫的反应机理，揭示反应过程中含硫基团的热变特性和有机硫的传质特征，研究反应动力学，揭示反应条件对脱硫效果的影响作用规律，优化反应条件；基于以上结论研究高硫焦中低温气相催化脱硫技术与常规石油焦高温（1200-1350℃）煅烧工艺的协同技术原型。该项目成果，将为开发节能环保型高硫焦气氛煅烧脱硫技术奠定理论基础。

针对当下石油焦含硫量普遍升高，高硫焦利用率低的情况，开发了高硫石油焦中低温气相催化脱硫工艺，并对石油焦中硫进行了多方面的研究。项目取得的成果包括：.① 研发了高效率的高硫焦在氨气气氛下的800 ℃煅烧脱硫工艺（脱硫率稳定超过>80%）；.② 构建了石油焦中存在最主要的四种杂质元素S-Na-V-Ca对石油焦反应性的综合影响模型，提出了四种元素相互催化影响的机理分析；.③ 构建了青岛石油焦大分子结构模型（C192H96O7N3S6），共计包含304个原子，展示了石油焦中的SNO元素官能团结构。构建了50×50×50Å的石油焦立体结构模型（C3717H1830N54O134S109），共计包含33934个原子，除以上功能外展示了石油焦的片层结构和分子间的结构关系；.④ 基于氨气脱硫工艺，开展了石油焦中硫在氨气气氛下下的脱出行为研究，对热力学和动力学机理进行了计算；.⑤ 对脱硫焦的应用进行了各种尝试，包括脱硫焦粉球团，发展到制备铝用炭素阳极、活性炭和碳化硅等方向。