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

日用化学工业（中英文） ›› 2024, Vol. 54 ›› Issue (5): 499-506.doi: 10.3969/j.issn.2097-2806.2024.05.001

• 基础研究 • 下一篇

基于密度泛函理论研究聚醚类破乳剂的构效关系

何海峰¹,孙立梅^2,^*(),杨风斌¹,刘凌枫³,王刚²,于滨²,吴达⁴

1.中国石油化工股份有限公司胜利油田分公司孤东采油厂，山东东营 257237
2.中国石油化工股份有限公司胜利油田分公司石油工程技术研究院，山东东营 257029
3.中国石油化工股份有限公司胜利油田分公司孤岛采油厂，山东东营 257231
4.山东大学胶体与界面化学教育部重点实验室，山东济南 250100

收稿日期:2023-07-29 修回日期:2024-04-19 出版日期:2024-05-22 发布日期:2024-05-21
基金资助:
中国石油化工股份有限公司项目(322035);中国石油化工股份有限公司胜利油田分公司项目(YC2201)

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

Haifeng He¹,Limei Sun^2,^*(),Fengbin Yang¹,Lingfeng Liu³,Gang Wang²,Bin Yu²,Da Wu⁴

1. Gudong Oil Production Plant, Sinopec Shengli Oilfield Company, Dongying, Shandong 257237, China
2. Petroleum Engineering Technology Research Institute of Sinopec Shengli Oilfield Company, Dongying, Shandong 257029, China
3. Gudao Oil Production Plant, Sinopec Shengli Oilfield Company, Dongying, Shandong 257231, China
4. Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, Shandong University, Jinan, Shandong 250100, China

Received:2023-07-29 Revised:2024-04-19 Online:2024-05-22 Published:2024-05-21
Contact: *E-mail: sunlimei866.slyt@sinopec.com.

摘要/Abstract

摘要：

油田采出液处理工艺中化学破乳剂的使用能够大大提升工作效率并且节约成本，其中聚醚类破乳剂的应用最为广泛，研究聚醚类破乳剂的构效关系对于新型破乳剂的研发及应用至关重要。本文首先对几种聚醚类破乳剂和反相破乳剂的破乳效果进行了评价和比较，然后根据沥青质分子的结构特点及现有聚醚类破乳剂和反相破乳剂的类型，选取了相应的模型分子，通过密度泛函理论（DFT）中B3LYP/6-31G基组得到其最优分子几何构型和静电势分布图，并利用泛函M062X/6-31G基组计算了聚醚类破乳剂模型分子分别与沥青质模型分子和水分子之间的相互作用能。结合聚醚类破乳剂和反相破乳剂的破乳性能评价结果，进而分析了聚醚类破乳剂的构效关系。结果表明，由理论化学计算结果所推测的破乳剂的破乳性能差异与其实际破乳效果相一致：具有支状结构、聚合度较高的聚醚类破乳剂的效果优于线型结构、聚合度较低的聚醚类破乳剂；酚醛树脂聚醚的破乳效果优于酚胺树脂聚醚，而反相破乳剂中则是多元醇聚醚类反相破乳剂的效果较优。该工作的开展表明采用密度泛函理论进行破乳剂的构效关系研究是可行的，能够为未来新型破乳剂的制备及选用奠定重要的理论基础和提供参考依据。

关键词: 原油, 破乳剂, 聚醚, 密度泛函理论, 构效关系

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

中图分类号:

TQ423

何海峰, 孙立梅, 杨风斌, 刘凌枫, 王刚, 于滨, 吴达. 基于密度泛函理论研究聚醚类破乳剂的构效关系[J]. 日用化学工业（中英文）, 2024, 54(5): 499-506.

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.

图/表 10

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参考文献 20

[1]	Gu Guojiang, Liu Ge, Chen Bin, et al. Research progress of physical emulsion breaking technology and device of W/O emulsion[J]. Chemical Industry and Engineering Progress, 2015, 34 (2) : 319-324.
[2]	Zhao Shanshan. Study on the stability of white oil-based oil-coated emulsion[D]. Jinan: Shandong University, 2020.
[3]	Zeng Haojian, Chang Zhen, Ji Wenxiong, et al. Study on the synthesis and demulsification of phenol-amine resin block polyether based on bisphenol A[J]. China Surfactant Detergent & Cosmetics, 2020, 50 (12) : 833-841.
[4]	Jiang Wei. Preparation and evaluation of acrylic acid-modified polyether[J]. Oilfield Chemistry, 2017, 34 (1) : 171-174.
[5]	Guo Rui, Ma Lijuan, Yan Yumeng, et al. Synthesis and application performance of acrylic-modified emulsion[J]. Fine Chemicals, 2020, 37 (7) : 1484-1492.
[6]	Chen Shi, Ling Zhang, Lei Xie, et al. Interaction mechanism of oil-in-water emulsions with asphaltenes determined using droplet probe AFM[J]. Langmuir, 2016, 32 (10) : 2302-2310. doi: 10.1021/acs.langmuir.5b04392 pmid: 26901396
[7]	Fu Yangyang, Meng Xianghai, Zhang Liping, et al. Adsorption behavior of hydrophobic-associated polymers at the oil-water interface[J]. Speciality Petrochemicals, 2020, 37 (1) : 19-23.
[8]	Li Xinxue, Lin Ruisen. Effect of oil-water interface behavior on demulsification of crude emulsion[J]. China Surfactant Detergent & Cosmetics, 2001 (6) : 14-15.
[9]	Li Meirong, Zhao Nana, Fang Hongbo, et al. The relationship between its structure and its effect and interface behavior[J]. Speciality Petrochemicals, 2012, 29 (5) : 62-66.
[10]	McArdle S, Endo S, Alán A, et al. Quantum computational chemistry[J]. Reviews of Modern Physics, 2020, 92: 1.
[11]	Cezar H M, Canuto S, Coutinho K. DICE: a monte carlo code for molecular simulation including the configurational bias monte carlo method[J]. Journal of Chemical Information and Modeling, 2020, 60 (7) : 3472-3488. doi: 10.1021/acs.jcim.0c00077 pmid: 32470296
[12]	Xin Wei, Han Jia, Hui Yan, et al. Novel insights on the graphene oxide nanosheets induced demulsification and emulsification of crude oil-in-water emulsion: A molecular simulation study[J]. Fuel, 2023, 333: 126529.
[13]	Prabhakar S, Melnik R. Influence of Mg²⁺, SO₄^2- and Na⁺ ions of sea water in crude oil recovery: DFT and ab initio molecular dynamics simulations[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2018, 539: 53-58.
[14]	Wang Zhechao, Li Shucai, Qiao Liping, et al. Finite element analysis of the hydro-mechanical behavior of an underground crude oil storage facility in granite subject to cyclic loading during operation[J]. International Journal of Rock Mechanics and Mining Sciences, 2015, 73: 70-81.
[15]	Li Chuncheng, Pu Hui, Zhong Xun, et al. Interfacial interactions between Bakken crude oil and injected gases at reservoir temperature: A molecular dynamics simulation study[J]. Fuel, 2020, 276: 118058.
[16]	Medvedev M G, Bushmarinov I S, Sun J W, et al. Density functional theory is straying from the path toward the exact functional[J]. Science, 2017, 355 (6320) : 49-52. doi: 10.1126/science.aah5975 pmid: 28059761
[17]	Zhao Liuchen, Zhang Hui, Wang Wangxu. Hydrogen bond association state of AEO₉ in 1, 2-propylene glycol,water and their mixed solvents[J]. China Surfactant Detergent & Cosmetics, 2016, 46 (12) : 671-676.
[18]	Zhang Hengming, Zhou Bing, Zhou Xia, et al. Molecular dynamics simulation of demulsification of O/W emulsion containing soil in direct current electric field[J]. Journal of Molecular Liquids, 2022, 361: 119618.
[19]	Ma Jun, Yang Yongli, Li Xingang, et al. Mechanisms on the stability and instability of water-in-oil emulsion stabilized by interfacially active asphaltenes: Role of hydrogen bonding reconstructing[J]. Fuel, 2021, 297: 120763.
[20]	Duan Ming, Song Xianyu, Fang Shenwen, et al. Layer-by-layer assembled film of asphaltenes/polyacrylamide and its stability of water-in-oil emulsions: A combined experimental and simulation study[J]. Journal of Physical Chemistry C, 2017, 121: 4332-4342.

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

基于密度泛函理论研究聚醚类破乳剂的构效关系

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

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