醇胺溶液CO2吸收过程反应机制

Reaction mechanisms during CO2 absorption in ethanolamine solutions

  • 摘要:
    目的 当前醇胺法CO2捕集存在能耗与成本较高的缺点,解决这一问题的主要方法是协同不同类型醇胺的吸收、解吸优势构建复合胺溶液。羟乙基乙二胺(AEEA)和N-甲基二乙醇胺(MDEA)是2种常用主吸收剂,其调配需要准确掌握CO2吸收规律,包括CO2负载量、产物离子浓度分布规律、反应级数等。目前对其吸收规律认识尚不足,相关反应参数缺乏,限制了工艺模型预测准确性。
    方法 研究AEEA和MDEA溶液CO2吸收过程,厘清其反应机理,并基于pH值法构建产物离子浓度分布模型,回归2种胺液的反应级数,确定反应速率模型。
    结果和结论 同一浓度AEEA溶液吸收容量和吸收速率均高于MDEA溶液。AEEA溶液CO2吸收过程呈现出两阶段特征,接近于二级反应。AEEA与CO2反应生成两性中间离子(R1R2NH+COO)是吸收过程的初始控制步骤,而其吸收后期为传质−反应共同控制阶段。MDEA溶液CO2吸收过程是碱催化水合过程,反应速率与MDEA浓度线性相关,为一级反应。基于所得新认识和模型,为碳捕集工艺中溶剂浓度、溶剂停留时间,溶剂循环量、塔器设计优化等提供理论指导。

     

    Abstract:
    Objective Presently, CO2 capture technology based on the ethanolamine solutions suffers from drawbacks such as high energy consumption and elevated costs. A primary method to address these challenges is to construct blended amine solutions by synergistically integrating the absorption and desorption advantages of different types of ethanolamines. Hydroxyethyl ethylenediamine (AEEA) and N-methyldiethanolamine (MDEA) represent two major commonly used absorbents, and their blending necessitates an accurate understanding of their CO2 absorption patterns, including CO2 loading capacity, the ion-concentration distribution patterns of reaction products, and reaction orders. Currently, their absorption mechanisms remain poorly understood, and there is a lack of relevant reaction parameters, jointly undermining the prediction accuracy of process models.
    Methods  By investigating the CO2 absorption processes of AEEA and MDEA solutions, this study clarified the reaction mechanisms of both solutions. Furthermore, it established ion concentration distribution models of the reaction products based on pH values, determined the reaction orders through regression analysis, and developed the reaction rate models of both solutions.
    Results and Conclusions  The results indicate that, under the same concentration, the AEEA solution exhibited higher CO2 absorption capacity and rates compared to the MDEA solution. The AEEA solution presented a two-stage CO2 absorption process, with reaction orders approaching 2. Initially, the CO2 absorption process in the AEEA solution was controlled by the formation of zwitterionic intermediates (R1R2NH+COO) from AEEA-CO2 reactions. In the late stage, this process was jointly governed by mass transfer and reactions. In contrast, the CO2 absorption in the MDEA solution was identified as a base-catalyzed hydration process, with the reaction rate showing a linear correlation with the MDEA concentration and the reaction order determined at 1. The novel insights and models of this study provide theoretical guidance for the optimization of the concentration, retention time, and circulation rate of solvents, along with column design, in carbon capture technique.

     

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