Phase separation prediction methodology for amine-based phase change absorbents based on reaction templates and molecular dynamics

doi:10.11949/0438-1157.20241178

Abstract

Abstract:

The development of carbon capture technology is crucial for mitigating global warming. Amine-based phase change absorbents are often used for chemical absorption of carbon dioxide due to their advantages such as low desorption energy consumption. However, the complexity of phase change absorbent formulations, unclear phase separation mechanisms, and high experimental costs limit the rapid development of novel high-performance phase change absorbents. To this end, this paper proposes a phase separation prediction methodology for amino-based phase change absorbents based on reaction templates and molecular dynamics. By constructing reaction templates, chemical absorption products are automatically generated. Molecular dynamic methods and indicators such as radial distribution functions are further employed to study the phase separation mechanisms of amino-based phase change absorbents and predict their phase separation behaviors. The proposed method is compiled into a fully automated software for predicting phase separation behaviors of phase change absorbents, complete with a visualization interface. This method has been applied to seven different phase change absorbent systems, with the predicted phase separation behaviors aligning with experimental results. It is also discovered that the hydrogen bonding interactions between organic solvents and water molecules are key factors influencing the phase separation behavior of phase change absorbents. The above studies assist in predicting the phase separation behavior of amino-based phase change absorbents from a computational perspective, which helps to reduce the cost of experimental testing and accelerate the development of novel high-performance phase change absorbents.

Key words: CO₂ capture, amine, phase change absorbent, molecular simulation, phase equilibrium

摘要：

碳捕集技术发展对于缓解全球变暖至关重要。胺基相变吸收剂凭借其解吸能耗小等优势，常用于化学吸收二氧化碳。然而，相变吸收剂配方成分复杂、分相机制不清、实验成本高昂，限制了新型高性能相变吸收剂的敏捷开发。对此，提出一种基于反应模板与分子动力学的胺基相变吸收剂分相预测方法，通过构建反应模板，自动生成化学吸收产物，进而利用分子动力学方法与径向分布函数等指标，研究胺基相变吸收剂的分相机制并预测其分相行为。所提方法编译为一套可全自动化预测相变吸收剂分相行为的软件及可视化界面，并应用于七种不同相变吸收剂体系，分相行为预测结果均与实验结果吻合，且发现有机溶剂与水分子之间的氢键作用是影响相变吸收剂分相行为的关键因素。本文研究成果可从计算角度辅助预测胺基相变吸收剂的分相行为，有助于降低实验测试成本，加速新型高性能相变吸收剂的开发。

关键词: 二氧化碳捕集, 有机胺, 相变吸收剂, 分子模拟, 相平衡

CLC Number:

TQ 028.8

Jianbing CHEN, Hao CHANG, Ming GAO, Bing XING, Lei ZHANG, Qilei LIU. Phase separation prediction methodology for amine-based phase change absorbents based on reaction templates and molecular dynamics[J]. CIESC Journal, 2025, 76(5): 2387-2396.

陈建兵, 常昊, 高明, 邢兵, 张磊, 刘奇磊. 基于反应模板与分子动力学的胺基相变吸收剂分相预测方法[J]. 化工学报, 2025, 76(5): 2387-2396.

Figures/Tables 9

Fig.1 The flowsheet of the phase separation prediction methodology for amino-based phase change absorbents

Fig.2 The software interface of SimuLab

Table 1 Compositions of CO2 phase change absorbent solutions and simulation results

组别	组分A （质量分数）	组分B （质量分数）	组分C （质量分数）	组分D （质量分数）	温度/K	实验结果	模拟结果
1	30% MEA	40% 正辛醇	20% NMP	10% 水	313.15	分相	X=20%、50%、80%均分相
2	30% MEA	5% 正辛醇	55% NMP	10% 水	313.15	不分相	X=20%、50%、80%均不分相
3	30% MDEA	30% 正庚醇	15% NMP	20% 水	313.15	分相	X=20%、50%、80%均分相
4	5% DEA	25% MDEA	40% 环丁砜	30% 水	313.15	分相	X=20%、50%、80%均分相
5	5% AMP	25% MDEA	40% 环丁砜	30% 水	313.15	分相	X=20%、50%、80%均分相
6	5% PZ	25% MDEA	40% 环丁砜	30% 水	313.15	分相	X=50%、80%分相，X=20%不分相
7	30% MEA	10% 正辛醇	50% NMP	10% 水	313.15	分相	X=80%分相，X=20%、50%不分相

Fig.3 The structures of molecular dynamic simulation before and after reaction for group 3 [(a) the initial structure; (b) the structure after simulation; X=50%]

Fig.4 The quantity variations for water molecules

Fig.5 The radial distribution function for group 1 (X=50%)

Fig. B1 The structures of molecular dynamic simulation before and after reaction for group 1, 2, 4, 5, 6, 7 [(a) is the initial structure; (b) is the structure after simulation; groups 1, 2, 4, 5, 6: X=50%; group 7: X=80%]

Fig.C1 The quantity variations for water molecules in group 3, 4, 5

Fig. D1 The radial distribution function for group 2—7 (groups 2—6: X=50%; group 7: X=80%)

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