Balaji Sayee Prasaad, Gangarapu Satesh, Ramdin Mahinder, Torres-Knoop Ariana, Zuilhof Han, Goetheer Earl L V, Dubbeldam David, Vlugt Thijs J H
Engineering Thermodynamics, Process & Energy Department, Faculty of Mechanical, Maritime, and Materials Engineering, Delft University of Technology , Leeghwaterstraat 39, 2628CB Delft, The Netherlands.
Laboratory of Organic Chemistry, Wageningen University , Dreijenplein 8, 6703HB Wageningen, The Netherlands.
J Chem Theory Comput. 2015 Jun 9;11(6):2661-9. doi: 10.1021/acs.jctc.5b00160.
Molecular simulations were used to compute the equilibrium concentrations of the different species in CO2/monoethanolamine solutions for different CO2 loadings. Simulations were performed in the Reaction Ensemble using the continuous fractional component Monte Carlo method at temperatures of 293, 333, and 353 K. The resulting computed equilibrium concentrations are in excellent agreement with experimental data. The effect of different reaction pathways was investigated. For a complete understanding of the equilibrium speciation, it is essential to take all elementary reactions into account because considering only the overall reaction of CO2 with MEA is insufficient. The effects of electrostatics and intermolecular van der Waals interactions were also studied, clearly showing that solvation of reactants and products is essential for the reaction. The Reaction Ensemble Monte Carlo using the continuous fractional component method opens the possibility of investigating the effects of the solvent on CO2 chemisorption by eliminating the need to study different reaction pathways and concentrate only on the thermodynamics of the system.
分子模拟用于计算不同CO₂负载量下CO₂/单乙醇胺溶液中不同物种的平衡浓度。在反应系综中，采用连续分数组分蒙特卡罗方法，在293K、333K和353K的温度下进行模拟。计算得到的平衡浓度与实验数据高度吻合。研究了不同反应途径的影响。为了全面理解平衡物种形成，考虑所有基元反应至关重要，因为仅考虑CO₂与MEA的总反应是不够的。还研究了静电作用和分子间范德华相互作用的影响，结果清楚地表明反应物和产物的溶剂化对反应至关重要。使用连续分数组分方法的反应系综蒙特卡罗方法，通过无需研究不同反应途径而仅专注于系统的热力学，开启了研究溶剂对CO₂化学吸附影响的可能性。
