基于密度泛函理论研究聚醚类破乳剂的构效关系

doi:10.3969/j.issn.2097-2806.2024.05.001

Abstract

Abstract:

The use of chemical demulsifiers in the treatment process of crude oil dehydration can greatly improve work efficiency and save costs. Among them, polyether demulsifiers are the most widely used, and studies on their structure-function relationship are crucial for the development and application of new demulsifiers. In this work, the demulsification effects of several polyether demulsifiers and reverse demulsifiers were evaluated and compared. Then corresponding model molecules were selected according to the structural characteristics of asphaltene molecules and the categories of polyether demulsifiers and reverse demulsifiers. Their optimal molecular geometries and electrostatic potential distribution diagrams were obtained through the B3LYP/6-31G basis set in density functional theory （DFT）. The interaction energy between a polyether demulsifier model molecule and an asphaltene model molecule, and the interaction energy between a polyether demulsifier model molecule and a water molecule, were both calculated using the functional M062X/6-31G basis set for several kinds of polyether demulsifiers. Combined with the evaluation results of demulsification performance of polyether demulsifiers and reverse demulsifiers, their structure-function relationships were analyzed. It shows that the difference in the demulsification performance of demulsifiers deduced from theoretical chemical calculation is consistent with their demulsification effects experimentally measured. Those polyether demulsifiers with branched structure and higher polymerization degree have better demulsification effects than those with linear structure and lower polymerization degree. In addition, polyether-grafted phenolic resin has better demulsification effect than polyether-grafted phenol-amine resin. Among the inverse demulsifiers investigated, polyol polyether inverse demulsifier has the best demulsification effect. Therefore, it is feasible to study the structure-function relationship of demulsifiers with DFT method, which can provide theoretical basis and reference for the preparation and selection of new demulsifiers in future.

Key words: crude oil, demulsifier, polyether, density functional theory, structure-function relationship

CLC Number:

TQ423

Haifeng He, Limei Sun, Fengbin Yang, Lingfeng Liu, Gang Wang, Bin Yu, Da Wu. Studies on the structure-function relationship of polyether-type demulsifiers based on density functional theory[J].China Surfactant Detergent & Cosmetics, 2024, 54(5): 499-506.

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References 20

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破乳剂的类型	破乳剂代号	破乳剂的结构特征
反相破乳剂	PR-701	长链醇聚醚
	PR-702	长链醇聚醚
	PR-302B	多元醇聚醚
破乳剂	PR-205	线型酚胺树脂聚醚
	PR-106	线型酚胺树脂聚醚（聚合度较高）
	CR-201	支状酚胺树脂聚醚
	CR-C07	支状酚醛树脂聚醚

分子间相互作用	?E/ （kJ/mol）
短链醇聚醚模型分子-沥青质模型分子	-56.40
长链醇聚醚模型分子-沥青质模型分子	-59.66
多元醇聚醚模型分子-沥青质模型分子	-73.67
线型酚胺树脂聚醚模型分子-沥青质模型分子	-80.95
支状酚胺树脂聚醚模型分子-沥青质模型分子	-114.7
线型酚胺树脂聚醚（聚合度较高）模型分子-沥青质模型分子	-86.46
线型酚醛树脂聚醚模型分子-沥青质模型分子	-95.95

分子间相互作用	?E/ （kJ/mol）
短链醇聚醚模型分子-水	-80.37
长链醇聚醚模型分子-水	-48.46
多元醇聚醚模型分子-水	-51.87
线型酚胺树脂聚醚模型分子-水	-53.30
支状酚胺树脂聚醚模型分子-水	-115.9
线型酚胺树脂聚醚（聚合度较高）模型分子-水	-68.56
线型酚醛树脂聚醚模型分子-水	-54.68

药剂	破乳剂代号	破乳剂的类型	理论计算结果预测	脱水率/除油率/%
反相破乳剂	PR-701	长链醇聚醚	多元醇效果最优	28
	PR-702	长链醇聚醚		52
	PR-302B	多元醇聚醚		57
破乳剂	PR-205	线型酚胺树脂聚醚	①支状酚胺树脂聚醚>线型酚胺树脂聚醚 ②聚合度较高的线型酚胺树脂聚醚>聚合度较低的线型酚胺树脂聚醚 ③酚醛树脂聚醚>酚胺树脂聚醚	37
	PR-106	线型酚胺树脂聚醚（聚合度较高）		55
	CR-201	支状酚胺树脂聚醚		58
	CR-C07	支状酚醛树脂聚醚		61

Studies on the structure-function relationship of polyether-type demulsifiers based on density functional theory

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