沥青质分子缔合作用机制、表征、理论计算与应用研究进展

doi:10.11949/0438-1157.20230583

摘要/Abstract

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

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

中图分类号:

TE 621

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.

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.

图/表 15

图1 沥青质分子及其缔合作用的主要研究领域[4-15]

Fig.1 Major areas of research on asphaltene molecules and their aggregation[4-15]

图2 (a) 大陆模型和群岛模型[17-19]；(b) 常用的沥青质分子模型[4,23-24]

Fig.2 (a) Continental model and archipelago model[17-19]; (b) Commonly used asphaltene molecular models[4,23-24]

表1 沥青质分子缔合聚集体模型的研究历程和主要观点

Table 1 Research history of asphaltene molecular association aggregation model and main perspectives

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

图3 Yen-Mullins模型[37]

Fig.3 Yen-Mullins model[37]

图4 沥青质分子的四种构象(a)[48-49]和三种堆叠构型(b)[50-51]

Fig.4 Four conformations (a)[48-49] and three stacking configurations (b)[50-51] of asphaltene molecule

图5 沥青质的超分子组装模型[5]

Fig.5 Supramolecular assembly models for asphaltenes[5]

图6 (a) σ-空穴和π-空穴[64]；(b) 氢键与π-氢键

Fig.6 (a) σ-hole and π-hole[64]; (b) Hydrogen bonding and π-hydrogen bonding

图7 (a) 独立梯度模型等值面面积分析图[7]；(b) HOMO-LUMO间隙（Δε）分析图[57]；(c) 侧链对π-π堆叠强度的影响机制[75]；(d) 沥青质与卟啉的聚集方式：钒卟啉（上）；镍卟啉（下）[65]

Fig.7 (a) Independent gradient model isosurface area analysis plot[7]; (b) HOMO-LUMO gap (Δε) analysis plot[61]; (c) Mechanism of sidechain on π-π stacking strength[75]; (d) The aggregation of asphaltenes and porphyrins: vanadium porphyrin (top); nickel porphyrin (lower)[65]

表2 表征沥青质的性质指标及技术手段

Table 2 Characterization techniques and indicators for asphaltenes

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

表2 表征沥青质的性质指标及技术手段

Table 2 Characterization techniques and indicators for asphaltenes

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

图8 (a) AFM用于测量含有不同沥青质浓度的油固界面相互作用力的示意图[195]；(b) 沥青质稳定乳液滴的Cryo-SEM图像[6]；(c) QCM-D的工作原理示意图[196]

Fig.8 (a) Schematic diagram of the AFM used to measure the interaction force at the oil-solid interface containing different asphaltene concentrations[195]; (b) Cryo-SEM image of droplets of emulsion stabilized by asphaltene: untreated asphaltenes[6]; (c) Working principle of QCM-D[196]

图9 沥青质分子缔合聚集的理论计算方法汇总[7-11]

Fig.9 Summary of theoretical calculation methods for associative aggregation of asphaltene molecules[7-11]

图10 (a) 沥青质聚集体在吸附剂表面通过各自的活性位点的吸附作用示意图[139]；(b) C5Pe在固体-水、固体-甲苯体系中的密度曲线及聚集体大小变化图[217]；(c) 表面活性剂促进油固分离示意图[12]

Fig.10 (a) Schematic diagram of the adsorption of asphaltene aggregates through their respective active sites on the adsorbent surface[139]; (b) Density profiles of C5Pe in solid-water and solid-toluene systems and changes of aggregate size[217]; (c) Schematic diagram of surfactant promoting oil-solid separation[12]

图11 (a) 沥青质沉积物堵塞管道图[15]；(b) 沥青质-酰胺型添加剂的静电势面[221]

Fig.11 (a) Asphaltene deposits clogging pipeline diagram[15]; (b) Analysis diagram of electrostatic potential surface of asphaltene-amide additives[221]

图12 (a) 在油/水界面形成沥青质保护膜的示意图[224]；(b) MJTJU-2的结构优势和破乳的界面过程[7]

Fig.12 (a) Schematic diagram of the formation of an asphaltene protective film at the oil/water interface[224]; (b) Structural advantages of MJTJU-2 and the interface process of demulsification[7]

图13 (a) 沥青质、沥青质与FI-2、沥青质与FI-5的SEM图[14]；(b) 沥青质与一系列离子流体形成的超分子复合体[233]；(c) 加入降黏剂前后重油的表观黏度变化与机理研究示意图[234]；(d) 沥青质模拟体系中的氢键结构[235]

Fig.13 (a) SEM images of asphaltene, asphaltene and FI-2, asphaltene and FI-5[14]; (b) Supramolecular complexes formed by asphaltenes with a series of ionized fluid[233]; (c) Apparent viscosity change of heavy oil before and after adding viscosity reducer and schematic diagram of the mechanism[234]; (d) Structures of hydrogen bonds in the simulation system of asphaltene[235]

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