Advances in molecular mechanisms, characterization, theoretical calculation and applications on asphaltenes aggregation

doi:10.11949/0438-1157.20230583

Abstract

Abstract:

The phenomenon of asphaltene association and aggregation in petroleum has an important impact on the exploitation, upgrading, storage and transportation of petroleum (especially unconventional petroleum ores such as heavy oil or tight oil reservoirs). The aggregation of asphaltene molecules directly determines the physical and interfacial properties of crude oil, which is the main cause of adsorption and deposition of petroleum components on the surface of minerals or pipeline walls, emulsification of oil and water (solid), and high viscosity of crude oil. This article systematically reviews the phenomenon and theoretical development of intermolecular association of asphaltene, explores the mechanism of asphaltene molecular association and aggregation from the perspective of non covalent interactions between molecules, and elaborates on the decisive influence of non covalent interactions dominated by electrostatic and dispersion on asphaltene association and aggregation. On this basis, the current status and development direction of the application of theoretical computation and interfacial characterization techniques on the study of asphaltene interfacial phenomena are summarized. Finally, based on the theory and phenomenon of asphaltene molecular association, the application of asphaltene association in the fields of solid surface adsorption and desorption, precipitation and dispersion, emulsion breaking technology development and viscosity reduction technology development has been discussed.

Key words: asphaltene aggregation, molecular simulation, interfacial characterization, non-covalent interactions, hydrogen bond, π-π stacking

摘要：

石油中沥青质分子的缔合聚集现象对于石油（尤其是重质油或致密油藏等非常规石油）的开采、储运、加工等具有重要影响，直接决定了原油的体相和界面性质，是矿物或管道器壁表面石油组分吸附沉积、油水（固）乳化、原油高黏等现象的主要成因。系统地综述了沥青质分子间缔合现象及理论发展，从分子间非共价相互作用角度探究了沥青质分子缔合聚集的作用机制，阐述了静电与色散作用主导的非共价相互作用对于沥青质缔合聚集的决定性影响规律。在此基础上，总结了近年来分子模拟等理论计算与界面表征技术在沥青质界面现象研究中的应用现状与发展方向。最后，基于沥青质分子缔合现象与理论，探讨了其在固体表面吸脱附、沉积、分散、破乳技术开发、降黏技术开发等领域的应用与思考。

关键词: 沥青质分子缔合聚集, 分子模拟, 界面表征, 非共价相互作用, 氢键, π-π堆叠

CLC Number:

TE 621

Huimin ZHOU, Ying TIAN, Siyi LIU, Jiahang ZOU, Runze ZHANG, Changqing HE, Lin HE, Hong SUI. Advances in molecular mechanisms, characterization, theoretical calculation and applications on asphaltenes aggregation[J]. CIESC Journal, 2023, 74(10): 3995-4019.

周惠敏, 田莹, 刘思亿, 邹佳航, 张润泽, 贺常晴, 何林, 隋红. 沥青质分子缔合作用机制、表征、理论计算与应用研究进展[J]. 化工学报, 2023, 74(10): 3995-4019.

Figures/Tables 15

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模型名称	主要观点	重要研究节点
Yen-Mullins层次结构模型	沥青质分子缔合包括分子、纳米聚集体、团簇三个层次	1961年，Yen等开始探究沥青质缔合体结构^[35]，1967年提出沥青的微观结构模型^[36]；2010年，Mullins^[37]提出Yen-Mullins层次结构模型；2011年，Mullins^[38]综述了Yen-Mullins层次结构模型的系统表征框架
超分子模型	沥青质分子缔合体由多种分子间相互作用形成稳定的超分子结构	1984年和2001年，Hirschberg等^[39]和Agrawala等^[40]提出了沥青质聚集的线性聚合机制；2011年，Gray等^[5]提出沥青质的超分子模型
溶解度模型	沥青质聚集体中位于核心的低溶解度组分A₁型分子，被高溶解度组分A₂型分子和溶剂介质包围	2001年，Gutiérrez等^[41]提出沥青质的溶解度模型；2008年，Acevedo等^[42]采用冷冻断裂和透射电子显微镜（TEM）技术证明了溶解度假说
空间胶体模型	沥青质吸附胶质分子并分散在油相中，吸附态胶质分子防止沥青质形成更大的聚集体	1997年，Barre等^[43]使用X射线和中子小角度散射技术推导了胶束尺寸多分散性和重均分子量；2001年，Murgich等^[44]提出沥青质和胶质分子的简单胶束体系可以是沥青质和胶质形成的固体颗粒，也可以是寿命很短的松散结合的胶束

模型名称	主要观点	重要研究节点
Yen-Mullins层次结构模型	沥青质分子缔合包括分子、纳米聚集体、团簇三个层次	1961年，Yen等开始探究沥青质缔合体结构^[35]，1967年提出沥青的微观结构模型^[36]；2010年，Mullins^[37]提出Yen-Mullins层次结构模型；2011年，Mullins^[38]综述了Yen-Mullins层次结构模型的系统表征框架
超分子模型	沥青质分子缔合体由多种分子间相互作用形成稳定的超分子结构	1984年和2001年，Hirschberg等^[39]和Agrawala等^[40]提出了沥青质聚集的线性聚合机制；2011年，Gray等^[5]提出沥青质的超分子模型
溶解度模型	沥青质聚集体中位于核心的低溶解度组分A₁型分子，被高溶解度组分A₂型分子和溶剂介质包围	2001年，Gutiérrez等^[41]提出沥青质的溶解度模型；2008年，Acevedo等^[42]采用冷冻断裂和透射电子显微镜（TEM）技术证明了溶解度假说
空间胶体模型	沥青质吸附胶质分子并分散在油相中，吸附态胶质分子防止沥青质形成更大的聚集体	1997年，Barre等^[43]使用X射线和中子小角度散射技术推导了胶束尺寸多分散性和重均分子量；2001年，Murgich等^[44]提出沥青质和胶质分子的简单胶束体系可以是沥青质和胶质形成的固体颗粒，也可以是寿命很短的松散结合的胶束

测试内容		技术手段
沥青质分子	分子量	蒸气压渗透法（VPO）^[47,103]、高效液相色谱法^[104-106]、气相色谱法^[107-108]、激光解吸质谱^[109-110]、基质辅助激光解吸电离质谱^[109-111]、表面辅助激光解吸电离质谱^[2]、傅里叶变换离子回旋共振质谱^[112-113]、电喷雾电离傅里叶变换离子回旋共振质谱^[114-115]、场电离质谱^[109]、电喷雾电离质谱^{[110,116-117]}、大气压化学电离质谱^{[106,116,118]}、大气压光电离质谱^{[109-110,116,119]}、激光诱导声学解吸质谱^[120-121]、飞行时间质谱（TOF MS）^[122-124]、电感耦合等离子体质谱^[125-126]、时间分辨荧光去偏振（TRF D）^{[22,109,127-130]}、荧光相关光谱（FCS）^[22,131-132]、高分辨率TEM^[133-134]、AFM^{[110,135-138]}、SAXS和SANS^[139-141]、FD^{[130,142-143]}、AFM-SEM^[144-145]等
	化学结构、构型	X射线吸收近边缘结构光谱^[146-147]、泰勒分散^[148]、激光解吸质谱、电感耦合等离子体质谱、电子顺磁共振波谱（EPR）^[106,149]、电子自旋共振光谱（ESR）^[150]、红外光谱（IR）、近红外光谱（NIR）^{[138,151-152]}、拉曼光谱（RA）、X射线拉曼光谱^[109-110]、钌离子催化氧化^[153-154]、荧光光谱（FS）^{[128,130,155-156]}、扩散有序波谱^{[107,157-158]}、FTIR、STM、TOF MS、XRD、XPS、SEM、TEM、AFM、SAXS和SANS、TRF D、FCS、NMR、FD等
	分子尺寸	紫外-可见吸收光谱法（UV-VIS）^[159-160]、近紫外-可见光吸收光谱^[161]、EPR、ESR、TRF D、FCS、FD等
沥青质聚集体	聚集现象	光致发光光谱^[162]、X射线拉曼光谱、超声波光谱^[163-164]、界面张力测试（IFT）^[165-166]、黏度测定^[167-168]、量热滴定^[169-170]、交流电导率/直流电导率^[171-172]、激光粒度分析仪^{[135,173-174]}、扩散有序波谱、近紫外-可见光吸收光谱、IR、NIRS、RA^{[138,175-176]}、XRD^{[156,177-178]}、SAXS和SANS、FS、UV-VIS、NMR、AFM-SEM、Cryo-SEM等
	临界点	超声波光谱、界面张力测试、离心^{[172,179-180]}、纳滤^[181-182]、激光粒度分析仪、扩散有序波谱、近紫外-可见光吸收光谱、FD、FS、UV-VIS、NMR等
	尺寸/形态	离心、纳滤、SEM、TEM、AFM、SAXS和SANS、TRF D、FCS、FD、AFM-SEM、Cryo-SEM等
分子间作用力	界面处分子取向、沥青质在固体表面吸附能等	和频光谱^[183-184]、QCM-D^[185-187]、AFM-SEM、Cryo-SEM等

测试内容		技术手段
沥青质分子	分子量	蒸气压渗透法（VPO）^[47,103]、高效液相色谱法^[104-106]、气相色谱法^[107-108]、激光解吸质谱^[109-110]、基质辅助激光解吸电离质谱^[109-111]、表面辅助激光解吸电离质谱^[2]、傅里叶变换离子回旋共振质谱^[112-113]、电喷雾电离傅里叶变换离子回旋共振质谱^[114-115]、场电离质谱^[109]、电喷雾电离质谱^{[110,116-117]}、大气压化学电离质谱^{[106,116,118]}、大气压光电离质谱^{[109-110,116,119]}、激光诱导声学解吸质谱^[120-121]、飞行时间质谱（TOF MS）^[122-124]、电感耦合等离子体质谱^[125-126]、时间分辨荧光去偏振（TRF D）^{[22,109,127-130]}、荧光相关光谱（FCS）^[22,131-132]、高分辨率TEM^[133-134]、AFM^{[110,135-138]}、SAXS和SANS^[139-141]、FD^{[130,142-143]}、AFM-SEM^[144-145]等
	化学结构、构型	X射线吸收近边缘结构光谱^[146-147]、泰勒分散^[148]、激光解吸质谱、电感耦合等离子体质谱、电子顺磁共振波谱（EPR）^[106,149]、电子自旋共振光谱（ESR）^[150]、红外光谱（IR）、近红外光谱（NIR）^{[138,151-152]}、拉曼光谱（RA）、X射线拉曼光谱^[109-110]、钌离子催化氧化^[153-154]、荧光光谱（FS）^{[128,130,155-156]}、扩散有序波谱^{[107,157-158]}、FTIR、STM、TOF MS、XRD、XPS、SEM、TEM、AFM、SAXS和SANS、TRF D、FCS、NMR、FD等
	分子尺寸	紫外-可见吸收光谱法（UV-VIS）^[159-160]、近紫外-可见光吸收光谱^[161]、EPR、ESR、TRF D、FCS、FD等
沥青质聚集体	聚集现象	光致发光光谱^[162]、X射线拉曼光谱、超声波光谱^[163-164]、界面张力测试（IFT）^[165-166]、黏度测定^[167-168]、量热滴定^[169-170]、交流电导率/直流电导率^[171-172]、激光粒度分析仪^{[135,173-174]}、扩散有序波谱、近紫外-可见光吸收光谱、IR、NIRS、RA^{[138,175-176]}、XRD^{[156,177-178]}、SAXS和SANS、FS、UV-VIS、NMR、AFM-SEM、Cryo-SEM等
	临界点	超声波光谱、界面张力测试、离心^{[172,179-180]}、纳滤^[181-182]、激光粒度分析仪、扩散有序波谱、近紫外-可见光吸收光谱、FD、FS、UV-VIS、NMR等
	尺寸/形态	离心、纳滤、SEM、TEM、AFM、SAXS和SANS、TRF D、FCS、FD、AFM-SEM、Cryo-SEM等
分子间作用力	界面处分子取向、沥青质在固体表面吸附能等	和频光谱^[183-184]、QCM-D^[185-187]、AFM-SEM、Cryo-SEM等

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