CN114446405A - 一种预测二氧化碳醇胺吸收剂分相行为的模型 - Google Patents
一种预测二氧化碳醇胺吸收剂分相行为的模型 Download PDFInfo
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- 238000005191 phase separation Methods 0.000 title claims abstract description 11
- 230000002745 absorbent Effects 0.000 title claims abstract description 10
- 239000002250 absorbent Substances 0.000 title claims abstract description 10
- 150000001450 anions Chemical class 0.000 claims abstract description 20
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000003775 Density Functional Theory Methods 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 230000002068 genetic effect Effects 0.000 claims description 2
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- 238000012417 linear regression Methods 0.000 claims 2
- 238000005457 optimization Methods 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 238000013528 artificial neural network Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
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- 229910052717 sulfur Inorganic materials 0.000 claims 1
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- 238000003077 quantum chemistry computational method Methods 0.000 abstract 1
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Abstract
本发明公开一种预测二氧化碳醇胺吸收剂分相行为的模型。该模型基于量子化学计算的定量构效研究方法，拟合出用于预测阴阳离子LogP的回归方程，以此阴阳离子的分配系数作为关键预测参数，建立二维坐标轴，作出分相预测线，获得预测吸收剂体系的两相区和单相区。该模型预测准确性高，适用范围广，可有效预测文献已报道的大部分二氧化碳醇胺吸收体系，对于新开发的相变吸收剂，可以用此方法判定是否会发生相变行为，有利于指导进一步相变吸收剂开发工作。
Description
技术领域
本发明属于新型化工环保领域，尤其涉及一种预测二氧化碳醇胺吸收剂分相行为的模型。
背景技术
全球变暖对人类未来的可持续性发展和地球生态***的稳定性产生了严峻的挑战，其主要原因是因为人类在社会生产实践活动中大量燃烧化石燃料并排放出了过量的CO2。减少CO2排放和降低大气中 CO2 浓度是解决全球变暖问题的两条主要路径。CO2 捕集、利用与封存技术(CCUS)被认为是目前 CO2 减排最有前景的技术方法。醇胺溶液具有 CO2吸收速率快、再生容易等特性，被广泛用于燃烧后 CO2 捕集(PCC)的研究。而相变吸收剂反应前为均相，反应后分为CO2贫相和二氧化碳富相，只需解析二氧化碳富相即可以达到解析再生的目的，可以达到节省再生能耗的目的，但目前实验室所研究的相变吸收剂都存在着各种各样的问题，如黏度大，CO2富相体积偏大等。目前，科研工作者一直致力于筛选和发展更好的相变体系，但是由于对相变机理尚不明确，一直没有一个快速有效的筛选方法。
发明内容
本发明的目的通过以下技术方案实现：
从文献中搜集与醇胺溶剂吸收二氧化碳产物（氨基甲酸盐和质子化胺）带有相同基团的阴阳离子（R-COO-）和（R-NH3+）在不同有机溶剂中的分配系数，用作初始建模计算。共收集了92组阴离子数据，其中包含了22种阴离子和14种有机溶剂，共收集了38组阳离子数据，其中包含15组阳离子和8种有机溶剂。
优选地， 作出分配系数数据中涉及的阴阳离子和对应溶剂的结构，静电势数据由密度泛函理论方法进行结构优化，使用明尼苏达密度泛函M062X，基组为6-311g++(d,p)，使用了iefpcm溶剂化模型及色散校正，算出电子云密度进行波函数分析，对每一个离子和溶剂提取14个静电势描述符，除此之外，对每一个溶质分子添加了常见的Druglikeness性质。
优选地， 去除相关系数大于0.95的共线性描述符以后，用于GFA遗传函数回归的方法对收集的数据进行回归，得到回归方程，对于阴离子的回归方程，提取了4个描述符，其中包含1个离子描述符和3个溶剂描述符，对于阳离子的回归方程，提取了4个描述符，其中包含2个离子描述符和2个溶剂描述符。
优选地，从文献中搜集已报道的醇胺+有机溶剂+水体系的分相/不分相数据，进行归纳整理。
优选地，将拟合得到的回归模型用于计算醇胺溶剂吸收二氧化碳的产物作图，获得分相/不分相的搭配组合阴阳离子有何规律。
发现分相与不分相的离子-溶剂搭配组合的分配系数具有很强的规律性，对于未曾报道的体系，亦可通过计算离子-溶剂搭配组合的分配系数判断是否分相。
附图说明
图1是实施实例1中阴离子回归所得模型。
图2是实施实例1中阳离子回归所得模型。
图3是实施实例1中相变行为预测图。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1：根据权利要求1中所述，将待预测的溶剂和离子分别使用量子化学软件进行结构优化，使用静电势分析软件对优化后的离子和溶剂进行静电势分析，提取静电势描述符，将静电势描述符带入所得模型，即可得知阴阳离子在该溶剂中的LogP，阴离子结果如图1，阳离子结果如图2，将计算所得的阴阳离子LogP 代入图3，通过点落入两相区还是单相区预测此醇胺-溶剂的搭配组合是否会发生相变。
Claims (9)
1.一种预测二氧化碳醇胺吸收剂分相行为的模型，其特征在于：
将醇胺+有机溶剂+水体系吸收二氧化碳反应前后物质分别通过量子化学方法（密度泛函理论）进行结构优化计算；提取计算结构的各类描述符；将所提取的描述符分别对阴阳离子的分配系数进行回归建模，获得阴阳离子分配系数的预测模型；根据阴阳离子分配系数建立图形预测。
2.对于权利要求1所述的醇胺+有机溶剂+水体系，其特征在于，醇胺包括伯胺、仲胺、叔胺类型等，有机溶剂包括醇类、醚类、酮类、含硫元素化合物等，醇胺/有机溶剂/水可以以任意比例互溶。
3.对于权利要求1所述的醇胺+有机溶剂+水体系吸收二氧化碳的反应前后物质，其特征在于以两性离子机理为反应机理，其对应产物的阴阳离子分别为氨基甲酸盐（R-COO-）和质子化胺（R-NH3+)。
4.对于权利要求1所述的量子化学方法（密度泛函理论）计算，其特征在于，采用不同量子化学软件进行计算，其中密度泛函方法采用不同的交换关联泛函（如LDA/GGA/B3LYP/PBE0/HSE06）等进行计算，使用了连续介质模型（如IEFPCM/SMD）及色散校正项（如GD3/GD3BJ）等，针对权利要求1中的基本体系开展结构优化、频率计算、能量计算以及电子密度计算等。
5.对于权利要求1所述提取计算结构描述符，其特征在于，提取描述符类型包括电子类描述符、量子化学描述符、拓扑类描述符及结构类描述符，.其中电子类描述符包括采用精确描述电荷分布性质的静电势描述符等。
6.对于权利要求1所述的对阴阳离子的分配系数进行数学建模，其特征在于：分别以阴离子在不同溶剂中的（如乙酸离子在甲醇/水之间）分配系数，阳离子在不同溶剂中的（如质子化的甲胺离子在甲醇/水之间）分配系数为目标参数。
7.采用统计学中的线性回归和非线性回归方法（如人工神经网络、遗传函数逼近、多元线性回归、最小二乘法）获得分配系数的预测模型。
8.对于权利要求1所述的阴阳离子分配系数建立图形预测，其特征在于，以预测获得阴离子分配系数和阳离子分配系数为坐标（包括阴离子分配系数为横坐标、阳离子分配系数为纵坐标，或阴离子分配系数为纵坐标、阳离子分配系数为横坐标等方式），获得图形，并设置单相和两相区域，其中两相区域表示该溶剂体系吸收CO2后存在相变分相关系。
9.对于权利要求1-7所述的模型，其特征在于经过对其应用域进行分析，其应用域非常广泛，适用于目前文献中所报道的大部分醇胺溶剂吸收二氧化碳后的产物和所用溶剂。
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