沥青质分子聚集体的解离对策

针对沥青质分子大芳环体系和多杂原子结构特征引起的π-π相互作用及氢键作用,运用量子力学、分子动力学等方法,研究沥青质分子聚集体的解离对策。对于π-π相互作用,从降低沥青质分子间π电子云重叠和减少沥青质分子的π电子数目两个方向研究解离措施;对于氢键作用,从降低沥青质分子间S—H、N—H、O—H间轨道叠加电子转移效应和减少沥青质分子的S、N、O数目两个方向研究解离措施。结果表明：引入π电子云分散剂可有效降低沥青质分子间π电子云重叠程度,对沥青质分子的稠合芳环进行局部加氢饱和可以减少其π电子数目,两条途径的分子模拟结果均能实现沥青质分子聚集体的解离;削弱沥青质分子间π-π相互作用对减弱氢键作用具有明显的促进作用;针对π-π相互作用的解离思路和措施也适应于金属卟啉分子与沥青质分子形成的聚集体,镍卟啉分子与沥青质分子形成的聚集体的解离难度比钒卟啉的大;提高温度加剧分子热运动及脱除杂原子可削弱或消除氢键作用,但在沥青质分子的其他芳环体系未改变的前提下,消除氢键作用不能实现对沥青质分子聚集体的完全解离。     

沥青质分子聚集体的聚集内因

运用量子力学、分子动力学等方法,研究沥青质分子聚集体形成过程的分子构型变化、能量变化以及电子分布情况。结果表明：沥青质分子形成聚集体过程中形变能很小,沥青质分子发生形变不是沥青质聚集体形成的决定因素,但为沥青质分子聚集进而形成聚集体提供基础,沥青质分子具有很强的本征聚集活性;沥青质分子间相互作用能很大,是沥青质分子聚集体形成的决定因素,其中,属于分子间固有属性的范德华力及泡利排斥作用之和相对较小,与沥青质分子结构特征相关的π π相互作用及氢键作用之和很大,表明由沥青质分子的大芳环体系和多杂原子的结构特征引起的π π相互作用及氢键作用是导致形成沥青质分子聚集体的主要原因;在所研究体系中,金属卟啉分子与含吡啶氮的沥青质分子通过π π相互作用而非轴向配位作用形成聚集体。     

塔河沥青质超分子体系的初步探索

以塔河沥青质作为研究对象,对沥青质的超分子体系进行了初步探索。采用动态光散射方法证明了沥青质可以在甲苯溶液中形成超分子结构,基于对沥青质分子结构的认识,利用分子模拟技术研究了形成沥青质超分子结构的分子间作用力,重点考察了氢键、酸碱作用、π-π相互作用以及沥青质分子和金属卟啉化合物之间的配位作用。在这几种分子间作用力中,沥青质分子间的π-π相互作用的能量最大,并随沥青质分子聚集数的增多而增大,是使沥青质形成超分子的最主要推动力。此外,采用甲基化改性方法去掉沥青质分子上的活泼氢,破坏沥青质分子间的氢键及酸碱作用,然后比较其聚集体与沥青质聚集体的差异;结果表明,前者的尺寸要明显小于后者的尺寸,说明通过活泼H而形成的分子间氢键以及酸碱作用与沥青质超分子的尺寸关系最为密切。     

氢键作用对沥青质超分子聚集的影响

对沥青质进行羧基化、磺化和甲基化反应,从加强与钝化氢键作用两个方面对比研究了不同化学处理对沥青质结构、热稳定性以及沥青质聚集的影响。研究发现：羧基、磺酸基等基团引入沥青质分子后,提高了沥青质分子的极性,增强了分子间的氢键作用,显著促进了沥青质的聚集,并且引入的基团极性越强,促进聚集效果越明显;相反,沥青质中含活泼氢官能团被甲基化后,甲基的引入屏蔽了形成氢键作用的基团,降低了沥青质聚集体形成过程中的氢键数量,从而削弱了沥青质的聚集。实验结果直观地证明了氢键作用对沥青质聚集体形成的影响,揭示了甲基化、羧基化及磺化反应影响沥青质聚集的机理。     

石油沥青质超分子聚集及解聚研究进展

石油沥青质组成复杂,氢/碳原子比低,硫、氮等杂原子含量高,给石油开采、运输和加工处理带来困难,究其原因是石油沥青质分子结构复杂,极易发生超分子聚集,形成聚集体。目前对沥青质超分子聚集的认识越来越广泛,并被石油化学工作者广泛接受。沥青质超分子聚集是通过电荷转移作用、偶极作用以及氢键作用形成沥青质分子之间的缔合,这些弱相互作用在石油体系的分子间普遍存在,实现沥青质聚集体的解聚是重质油高效轻质化的基础。研究表明,采用化学方法改变沥青质分子结构或采用物理方法改变沥青质物理状态,均能在一定程度上使得沥青质聚集体解聚。     

沥青质分子聚集体中氢键作用力的研究

为研究沥青质分子聚集体中的氢键作用,用量子力学与分子动力学相结合的方法对形成沥青质分子聚集体中的氢键进行了研究。结果发现,沥青质分子中含有的N、S、O等杂原子是沥青质分子形成氢键的必要条件;沥青质分子聚集体形成单个氢键的键能较小,但聚集体中含有多个氢键时,其分子间的作用力会大幅增加。沥青质分子形成氢键的本质是由于H原子与杂原子的价层轨道电子进行叠加形成的,沥青质分子间有极少量的电子转移,导致形成弱的次级键; 在氢键作用中,起主要作用的是轨道相互作用能和色散作用能。     

沥青质对原油乳状液的影响研究进展

沥青质作为原油中一类天然乳化剂,在稳定油水乳状液方面起到了重要作用,目前对沥青质油水界面膜的形成及稳定机理还没有统一的结论。综述了国内外沥青质对油水乳状液稳定性影响的有关研究现状与发展趋势,介绍了原油中以沥青质为主的天然乳化剂的存在形态与乳状液稳定性的关系、沥青质的分子结构和聚集体的特征及分子模拟方法在沥青质在油水界面成膜过程中的研究进展。     

沥青质分子聚集体中π-π相互作用的研究

采用量子力学与分子动力学相结合的方法对形成沥青质分子聚集体的分子间π-π相互作用进行了研究。结果表明：沥青质分子间的π-π相互作用能随着分子芳香环数的增加而增大;分子中含有的杂原子显著增加了沥青质分子间的π-π相互作用能;沥青质分子的支链长度及类型能够影响π-π相互作用能的大小;当沥青质分子聚集体中含有多个π-π相互作用时,其分子间的聚集作用力会大大增加;沥青质分子间形成π-π相互作用的过程中,分子间有少量的电子转移;色散作用是π-π相互作用中的主要作用。     

沥青质分子界面行为的耗散粒子动力学

运用耗散粒子动力学(DPD)方法模拟了“孤岛型”沥青质分子和其纳米聚集体在油-水界面的取向性、聚集行为,分析了富氧支链对沥青质分子取向性的影响。结果表明：存在油-水界面时,沥青质分子从油、水相中脱离,吸附在油-水界面处,稠芳环核与油-水界面平行,烷烃支链伸入油相;随着沥青质浓度升高,空间位阻作用使沥青质分子彼此分离,稠芳环核与界面存在夹角,直至部分沥青质被“挤出”界面;在π-π相互作用下,被“挤出”界面的稠芳环核与吸附在油-水界面的稠芳环核平行堆叠,距离约为0.5 nm,烷烃支链将稠芳环核包围;沥青质纳米聚集体由于被烷烃支链包裹,极易脱离油-水界面,溶于油相;富氧支链亲水性强,伸入水相,使稠芳环核与油-水界面产生夹角,甚至垂直;富氧支链会改变沥青质分子的取向性。     

沥青质在高定向热解石墨表面络合机制的分子动力学模拟

沥青质在固体表面的络合机制是解决剩余油开采难题的重要理论基础。为了给聚集抑制剂和表面活性剂的开发提供理论依据,采用分子动力学模拟,系统研究了沥青质在高定向热解石墨表面附着、聚集的特征。通过计算表面吸附过程中沥青质的自由能变化,基于Yen-Mullins模型的定量判据,结合沥青质平均相互作用分子数和分子密度分布,定量分析了沥青质在固-液界面体系与溶液体系中聚集作用的差异。分子动力学模拟分析表明,固体表面会降低沥青质的聚集程度,加快聚集过程中的阶段分化,具体包括4个阶段的界面过程：①沥青质覆盖固体表面并逐渐铺满一层;②固体表面上形成纳米聚集体;③固体表面上纳米聚集体与溶液中的纳米聚集体通过边缘堆叠、T形堆叠形成簇状物;④固体表面的聚集体与溶液中的聚集体通过脂肪侧链接触形成絮凝物。     

Developing a Scaling Equation as a Function of Pressure and Temperature to Determine the Amount of Asphaltene Precipitation

A simple and applicable scaling equation as a function of pressure, temperature, molecular weight, dilution ratio (solvent), and weight percent of precipitated asphaltene has been developed. This equation can be used to determine the weight percent of precipitated asphaltene in the presence of difference precipitants (solvents) and the amount of solvent at onset point. Since increasing the pressure of crude oil decreases the amount of asphaltene precipitation, the effect of reservoir pressure has been taken into account in developing this equation. The results obtained by using this equation are substantially different and more accurate from other developed scaling equations for asphaltene precipitation. By considering the effect of reservoir pressure in developing the scaling equation and application of a genetic algorithm, the unknown parameters of the scaling equation are simultaneously and without any reservation obtained. The most important application of this unique equation is in the determination of critical point of asphaltene precipitation, known as onset point, and asphaltene precipitation in gas injection operations for enhanced oil recovery. The results predicted using the scaling equations are compared with the authors' experimental and literature precipitation data and it is shown that they are in good agreement with our experimental data. The scaling equation can be used in the design of gas-injected reservoir to prevent precipitation of the asphaltene aggregates in the reservoir.     

MOLECULAR MECHANICS OF AGGREGATES OF ASPHALTENES AND RESINS OF THE ATHABASCA OIL

An analysis of the effects of an almost continuous chemical distribution of asphaltenes and resins on the molecular recognition processes occurring in crude oil indicates that their aggregates will have a broad distribution both in the chemical composition and in the strength of the intermolecular interactions responsible for the aggregation. Then, crude oil cannot be described just as a sol formed by solid asphaltene particles dispersed by resins or as a simple micellar system of asphaltene and resin molecules. The molecular aggregates may vary from solid particles formed by asphaltenes and resins to loosely bound micelles with quite short lifetimes. These different aggregates may coexist within the crude oil and many will exchange components with others. The entropic contributions to the changes in free energy upon aggregation were also discussed. Molecular mechanics calculations showed that a model asphaltene aggregate from Athabasca exhibits stronger interactions with its resins than with solvents such as toluene and n-octane. The resins showed a considerable selectivity for the different adsorption sites of the asphaltene aggregate. This selectivity was stronger than that found for the solvent molecules, indicating that it is enthalpically more favorable for them to form aggregates with the asphaltenes. The selectivity may also help to explain the specificity of some resins that are able to disperse only the asphaltenes of certain types of crude oils while failing to do the same for others.     

The Impact of CO2 Injection and Pressure Changes on Asphaltene Molecular Weight Distribution in a Heavy Crude Oil: An Experimental Study

Abstract

This work concerns observing the pressure as well as CO₂ mole percentage effects on asphaltene molecular weight distributions at reservoir conditions. A high-pressure, high-temperature asphaltene measurement setup was applied, and the amount of precipitated asphaltene at different pressures as well as CO₂ mole percentage in an Iranian heavy crude oil was measured. Moreover, the asphaltene molecular weight distributions during titration of crude oil with different n-alkanes were investigated. The gel permeation chromatography (GPC) apparatus was used for characterization of asphaltene molecular weight under different conditions. It has been observed that some thermodynamic changes such as pressure depletion above the bubble point increase the average molecular weight of asphaltene and cause the asphaltene molecular weight distributions changes from a bimodal curve with two maxima to a single maxima curve. One the other hand, below the bubble point, pressure reduction causes a decrease in the average molecular weight of asphaltene and also causes the shape of asphaltene molecular weight distributions to restore, which might be due to dissolution of asphaltene aggregates. An interesting result is that asphaltene molecular weight distribution at the final step of pressure reduction tests, ambient condition, shows approximately the same trend as the distribution of asphaltene molecular weight obtained at reservoir condition. This behavior explains the reversibility of the asphaltene precipitation process under pressure depletion conditions. In the case of CO₂ injection, the graphs of asphaltene molecular weight distributions always show a single modal trend and shift toward larger molecular weight values when CO₂ mole percentage increases. The results of this work can be imported to thermodynamic models that use polydisperse data of heavy organic fractions to enhance their performance at reservoir conditions. The distributions obtained by this method are good indicators of asphaltene structures at reservoir conditions.     

Structural Relaxation Behaviors of Three Different Asphaltenes Using MD Calculations

For asphaltene obtained from vacuum residues of three different kinds of crude oils (Khafji, Maya, and Iranian-Light), the energy-minimum conformation calculated by molecular mechanics-dynamics simulations showed that aggregated structures of asphaltene molecules through noncovalent interactions are the most stable conformation. Changes of aggregated structures by heating or solvent treatment were investigated by using the molecular dynamics calculation. For Khafji and Iranian-Light asphaltenes, the simulation showed that the aggregated structure was dissociated at 673K, while for Maya asphaltene the dissociation behavior was not observed, showing that Maya asphaltene seems difficult to be dissociated by heating, compared to other asphaltenes. In contrast, the simulation of relaxation of the Maya aggregates in quinoline showed that at 573K a part of aggregates was dissociated more easily than Khafji and Iranian-Light asphaltenes. These results above suggest that the effects of heating and solvent treatment on the structural relaxation of asphaltene aggregates can be different.     

Assembly of asphaltene molecular aggregates as studied by near-UV/visible spectroscopy: II. Concentration dependencies of absorptivities

The properties of molecular aggregation in toluene solutions of a crude oil and solid asphaltenes are determined almost solely by the concentration of asphaltenes, as shown by absorptivity measurements at 315–750 nm. From non-monotonic concentration dependencies of absorptivities, it is concluded that asphaltene monomers are abundant in solutions with asphaltene concentrations below 1–5 mg/l, while molecular aggregates are effectively formed above 20–25 mg/l. The most stable oligomers are a dimer and a dimer pair (Yen's “nanocrystallite” [NC]). Nanocrystallites act as building blocks for more complex aggregates at asphaltene concentrations exceeding 90–100 mg/l. These optical absorption results are supported by studies of Rayleigh scattering in asphaltene solutions.     

ASPHALTENE PRECIPITATION AND SOLVENT PROPERTIES OF CRUDE OILS

Improved prediction of the onset of asphaltene precipitation may be achieved using refractive index (RI) to characterize crude oils and their mixtures with precipitants and solvents. Experimental measurements of RI for mixtures of several crude oils with the precipitant n-heptane, are reported at ambient conditions. Theoretical developments are described that will permit extension of these observations to reservoir conditions

Measurements of RJ at the onset of precipitation have shown that the onset occurs at a characteristic RI for each oil/ precipitant combination, supporting the premise that precipitation is dominated by London dispersion interactions and thus, that RI can be used to predict the onset of precipitation. Reports in the literature showing that the onset of precipitation occurs at constant solvent-to-precipitant ratios provide additional confirmation

The theory is developed on the assumption that London dispersion forces dominate aggregation and precipitation of asphaltenes. The interaction energy of asphaltene molecules or aggregates in a medium of oil can be expressed as a function of the difference between the RI of asphaltene and oil. The RI of live crude oil during pressure depletion can be calculated from the RI of the stock tank oil, the molar refraction of the separator gas, the formation volume factor B_o and the solution gas/ oil ratio R_s     

Investigation into mechanisms and kinetics of asphaltene aggregation in toluene/n-hexane mixtures

Determining the rate of asphaltene particle growth is one of the main problems in modeling of asphaltene precipitation and deposition.In this paper,the kinetics of asphaltene aggregation under different precipitant concentrations have been studied.The image processing method was performed on the digital photographs that were taken by a microscope as a function of time to determine the asphaltene aggregation growth mechanisms.The results of image processing by MATLAB software revealed that the growth of asphaltene aggregates is strongly a function of time.Different regions could be recognized during asphaltene particle growth including reaction-and diffusion-limited aggregation followed by reaching the maximum asphaltene aggregate size and start of asphaltene settling and the final equilibrium.Modeling has been carried out to predict the growth of asphaltene particle size based on the fractal theory.General equations have been developed for kinetics of asphaltene aggregation for reaction-limited aggregation and diffusion-limited aggregation.The maximum size of asphaltene aggregates and settling time were modeled by using force balance,acting on asphaltene particles.Results of modeling show a good agreement between laboratory measurements and model calculations.