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    二氧化碳氧化丙烷脱氢制丙烯研究进展

    Research progress on oxidative dehydrogenation of propane to propylene by carbon dioxide

    • 摘要: 丙烯是重要的化工基础原料,可用于生产多种化工产品,传统的丙烯生产工艺难以满足日益增长的市场需求,利用页岩气或天然气中的丙烷生产丙烯是替代传统石油裂解工艺的重要环保路线。与已经工业化的丙烷直接脱氢(PDH)制丙烯技术相比,CO2氧化丙烷脱氢(CO2-ODHP)制丙烯不仅可以在较低的温度下实现丙烷的高效转化;同时可通过碳的气化反应(CO2+C=2CO)去除反应积碳,并有效抑制丙烯过度氧化(与O2相比),是一种更具工业应用潜力的高效丙烯生产技术。此外,CO2-ODHP工艺可直接通过化学转化降低酸性气体CO2的排放,具有显著的环境效益。从CO2-ODHP反应的热力学分析和反应机理入手,概括了CO2对催化剂内在活性的关键作用,综述了几种代表性的金属基催化剂体系(Pt基、Gr基、Ga基、V基、In基催化剂)在CO2-ODHP反应中的研究进展,讨论了CO2-ODHP催化剂上常见的失活行为。Pt基、Ga基、In基催化剂上的CO2-ODHP反应通常遵循PDH和逆水煤气耦合反应机理,而Gr基和V基催化剂上的CO2-ODHP反应通常遵循Mars-Van Kervelen氧化还原反应机理,催化剂的结焦、烧结和结构改变是CO2-ODHP反应中催化剂常见的失活原因。在此基础上,对未来CO2-ODHP催化剂的研究进行了展望,借助先进表征技术和理论计算深入研究反应机理是未来CO2-ODHP研究的重要方向,构建能有效活化CO2并选择性将丙烷转化为丙烯的双功能催化剂是CO2-ODHP反应实现工业化的关键。

       

      Abstract: Propylene is an important chemical industry raw material, which can be used to produce a variety of chemical products. In recent years, traditional routes to produce the propylene cannot fulfill the steady increasing demand for propylene. Utilizing propane from shale gas or natural gas to produce propylene represents an important environmentally friendly alternative to conventional petroleum cracking. Compared to the already industrialized direct dehydrogenation of propane (PDH), oxidative dehydrogenation of propane to propylene (CO2-ODHP) can not only realize the efficient conversion of propane at lower temperature, but also reduce coke deposition via the reverse Boudouard reaction.Compared with oxidative dehydrogenation of propane (O2-ODHP), CO2-ODHPcan effectively inhibit overoxidation of propylene, and it is a potentital approache to produce propylene. Additionally, CO2-ODHP reduces emissions of the acidic gas via chemical conversion, offering significant environmental benefits.In this review, we summarized the recent research progress of catalyst systems (Pt-, Gr-, Ga-, V-, and In-based metal catalysts), role of CO2, catalytic mechanism and deactivation mechanism in the CO2-ODHP. Typically, CO2-ODHP reaction on Pt-based, Ga-based, and In-based catalysts follows a mechanism coupling PDH and the reverse water-gas shift reaction. In contrast, Cr-based and V-based catalysts generally operate via a Mars-van Krevelen redox mechanism. Commonly, catalyst deactivation in CO2-ODHP is attributed to coking, sintering, and structural changes. We also present perspectives for future progress in the CO2-ODHP. In the future, it is crucial to clarify the catalytic mechanism through advanced characterizations and theoretical calculations. The development of a bifunctional catalyst capable of effectively activating CO₂ and selectively converting propane into propylene is key to the industrialization of the CO₂-ODHP reaction.

       

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