醇胺吸收剂二氧化碳解吸能耗构效关系分析

Elucidation of Structural Factors for Desorption Energy Consumption of CO₂ from Alcohol Amine Absorbents

摘要

为揭示醇胺化合物结构与二氧化碳（CO₂）解吸能耗的内在关联，为低能耗醇胺吸收剂设计提供理论依据，采用MaXFlow软件，基于密度泛函理论（DFT）的量子化学方法，对76种醇胺化合物在水溶液中的三维空间结构进行精准优化。计算了反映分子微观结构特征的关键参数，包括几何结构参数（振动频率、分子表面积、分子体积等）、电子结构参数（静电荷分布、前线轨道能量、偶极矩等）及各类化学指纹数据。在此基础上，通过数据特征提取与构效关系（QSPR）关联分析，对醇胺化合物的CO₂解吸能耗与其结构参数进行回归建模，建立了物理意义明确的定量关系方程。研究首次揭示：氮（N）原子静电荷、前线轨道能隙（HOMO-LUMO gap，L-H gap）和分子表面积是影响CO₂解吸能耗的核心结构因素，其影响规律为：N原子静电荷越负、L-H gap越窄、分子表面积越小，醇胺化合物的CO₂解吸能耗越高。该定量关系方程的决定系数（R²）达0.938，交叉验证决定系数（Q²）为0.923，表明模型具有优异的拟合度与较强的预测能力，可实现对醇胺化合物CO₂解吸能耗的精准预测。

Abstract

To elucidate the intrinsic relationship between the structure of alkanolamine compounds and the energy consumption of carbon dioxide (CO₂) desorption, thereby providing a theoretical basis for designing low-energy-consumption alkanolamine absorbents, MaXFlow software was employed to perform precise optimisation of the three-dimensional spatial structures of 76 alkanolamine compounds in aqueous solutions using quantum chemical methods based on density functional theory (DFT). Key parameters reflecting molecular microstructural characteristics were calculated, including geometric parameters (vibrational frequencies, molecular surface area, molecular volume, etc.), electronic structure parameters (electrostatic charge distribution, frontier orbital energies, dipole moments, etc.), and various chemical fingerprint data. Building upon this, data feature extraction and quantitative structure-property relationship (QSPR) correlation analysis were employed to regress the CO₂ desorption energy consumption of alkanolamine compounds against their structural parameters, establishing quantitatively meaningful equations. The study first revealed that the electrostatic charge of nitrogen (N) atoms and the HOMO-LUMO gap (L-H gap), and molecular surface area are core structural factors influencing CO₂ desorption energy consumption. The influence pattern is as follows: the more negative the N atom's electrostatic charge, the narrower the L-H gap, and the smaller the molecular surface area, the higher the CO₂ desorption energy consumption of the alkanolamine compound. The coefficient of determination (R²) for this quantitative relationship equation reached 0.938, with a cross-validation coefficient of determination (Q²) of 0.923. This indicates the model possesses excellent fitting capability and robust predictive power, enabling precise forecasting of CO₂ desorption energy consumption for alkanolamine compounds.

关键词

二氧化碳 / 结构参数 / 解吸能耗 / 定量关系

Key words

CO₂ / structural descriptor / desorption energy / quantitative relationship

参考文献

[1] 姜培学, 金红光 . 面向“双碳”目标的能源转化利用领域前沿交叉战略研究[J]. 科学通报, 2024, 69(34): 5007-5015.

[2] 盛依依 . 二氧化碳捕集技术研究及工业化进展[J/OL]. 现代化工, 2025, 45 (03): 56-60+65. https://link.cnki.net/urlid/11.2172.TQ.20250124.1313.043

[3] 何珊, 廖传华, 汪明星 . 二氧化碳资源化利用进展[J/OL]. 化工科技, 2025, 33 (02): 79-84. https://doi.org/10.16664/j.cnki.issn1008—0511.20250218.001

[4] 张克舫 . 醇胺吸收法燃煤电厂CO₂捕集系统能量分析及优化 [D]. 北京: 北京工业大学, 2015.

[5] 杨钧晗 . 二氧化碳变压吸附材料的研究进展[J]. 节能, 2024, 43(10): 126-128.

[6] 刘雨诗, 李晶晶, 唐晓东 . 离子液体吸收二氧化碳研究进展[J]. 精细石油化工, 2023, 40(6): 80-84.

[7] 李恩尚 . 聚酰亚胺基混合基质膜制备及CO₂分离性能研究 [D]. 天津: 天津大学, 2022.

[8] 盛荟霖, 胡大鹏, 魏炜 . 混合醇胺法吸收电厂烟气中CO₂的性能研究 [J]. 现代化工, 2024, 44(2): 177-189.

[9] 窦雅玲, 曹发 . 醇胺法在二氧化碳捕集中的应用发展综述[J]. 当代化工研究, 2024, 24(6): 18-20.

[10] 方梦祥, 王涛, 张翼 . 烟气二氧化碳化学吸收技术[M]. 北京: 化学工业出版社, 2023.

[11] 王乐萌 . 新型复配醇胺溶液捕集CO₂过程的吸收特性研究 [D]. 北京: 华北电力大学, 2018.

[12] 葛少辉 . 世界炼油工业发展趋势展望[J]. 中国石化, 2024, 24(12): 36-38.

[13] 高宁博, 王明晨, 杨天华 等 . 有机燃料燃烧烟气的二氧化碳捕集技术研究[J]. 洁净煤技术, 2024, 30(2): 562-572.

[14] 金伟, 李贵弘, 阮虹嘉 等 . 碳中和目标下二氧化碳捕集路径及技术研究进展[J]. 昆明理工大学学报, 2024, 49(3), 265-274.

[15] 刘竞文, 孙乐乐, 刘健 等 . 有机胺CO₂吸收液催化解吸研究进展 [J]. 低碳化学与化工, 2025, 50(1): 120-131.

[16] Prachi Singha, Geert F Versteeg . Structure and activity relationships for CO₂ regeneration from aqueous amine—based absorbents [J]. Chemical Engineering Science, 2008, 86: 347-359.

[17] Jochen Oexmann, Alfons Kather . Minimising the regeneration heat duty of post—combustion CO₂ capture by wet chemical absorption: The misguided focus on low heat of absorption solvents [J]. International Journal of Greenhouse Gas Control, 2010, 4: 36-43.

[18] 程静星, 鲁厚芳, 岳海荣 等 . 醇胺溶液二氧化碳解吸能力的定量构效关系研究[J]. 低碳化学与化工, 2019, 44(6): 70-75.

[19] Box G E, Hunter W G, Hunter J S . Statistics For Experimenters: An introduction to Design, Data Analysis, and Model Building, Wiley Series in Probability and Mathematical Statistics[M], John Wiley & Sons: New York, 1978.

[20] Draper N R, Smith H . Applied Regression Analysis [M], Wiley—Interscience: Weinheim, 1998.

[21] Friedman J H . Multivariate Adaptive Regression Splines, Technical Report No. 102[M], Stanford University: Stanford, 1990.

[22] Stanton D, Jurs P . Development and use of charged partial surface area structural descriptors in computer assisted quantitative structure property relationship studies[J]. Analytical Chemistry, 1990, 62: 2323-2329.

[23] Wiener H. Structural Determination of Paraffin Boiling Points[J] J. Chem. Phys., 1947, 69: 17-20.

[24] Muller W R . An Algorithm for Construction of the Molecular Distance Matrix[J]. J. Comput. Chem., 1987, 8: 170-173.

[25] Bonchev D. Information Theoretic Indices for Characterization of Chemical Structures[M]. Chemometrics Series, Vol. 5, New York, Research Studies Press Ltd., 1983.

[26] Hall L H, Kier L B . Electrotopological State Indices for Atom Types: A Novel Combination of Electronic, Topological and Valence State Information[J]. J. Chem. Inf. Comput. Sci., 1995, 35: 1039-1045.

[27] MaXFlow 分子模拟与人工智能平台 . https://www.neotrident.com/platform/maxflow.html, Digital Transformation & Intelligent Innovation.

[28] Topliss J G, Edwards R P . Chance Factors in Studies of Quantitative Structure—Activity Relationships[J]. J. Med. Chem., 1979, 22: 1238-1247.

[29] Stahle L, Wold S . Progress of Medical Chemistry, Vol. 25[M]. Elsevier: Amsterdam, 1988.

基金资助

中国石油重大基础研究专项资助“二氧化碳规模化捕集、驱油与埋存全产业链关键技术研究及示范”(2021ZZ01-01)

石油基炭材料的构筑和功能化研究(2023ZZ33-1)

电子级PI薄膜产业链基础研究及全产业化开发(23-10A-01-05-03)