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。     

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。     

沥青质聚集体的解聚分离方法综述和探析

沥青质在原油、渣油体系中常以分子聚集体的形式存在,要研究沥青质的分子组成和结构以及含沥青质重油的加工,基础是要实现沥青质分子聚集体的解聚、分离。基于此,针对沥青质分子聚集体中存在的分子间相互作用（力）,从良溶剂稀释、消除聚集作用位点、适度热作用、超声波作用及碰撞诱导解离等五个方面阐述了沥青质分子聚集体解离方法及进展,进一步介绍了基于沥青质分子极性、分子尺寸、酸碱性以及反应性等方面开展沥青质分子水平分离的方法及进展。     

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。     

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。     

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。     

减压渣油微观相结构特性的分子模拟

选用4种模型化合物代表减压渣油四组分(SARA),采用分子动力学模拟了减压渣油微观相结构,发现不同结构分子间相互作用的差异是减压渣油微观非均匀分布的本质原因,并通过电子分布特性分析了不同结构分子间相互作用差异的本质原因。沥青质分子间强相互作用使得沥青质分子自缔合形成聚集体;而多个胶质分子与沥青质分子的强相互作用封闭了沥青质分子自身进一步发生相互作用的活性位;同时,与胶质分子、饱和烃分子具有强相互作用的芳香烃分子将沥青质 胶质分子形成的聚集体分散在由芳香烃 饱和烃分子构成的连续相内,其中芳香烃分子更靠近胶质分子。因此,增加沥青质、饱和烃分子的含量会促进沥青质聚集,降低减压渣油稳定性;增加胶质、芳香烃分子的含量会阻碍沥青质聚集,提高减压渣油稳定性。     

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。     

原油乳状液稳定机理的分子模拟研究

沥青质在稳定原油乳状液方面发挥重要的作用,采用分子动力学研究了沥青质分子在甲苯 水界面的吸附聚集行为,用量子化学方法研究了沥青质和水分子间以及沥青质分子之间的相互作用能,探讨了沥青质稳定乳状液的作用机理。结果表明,沥青质分子和水分子间氢键的形成是沥青质能够在油 水界面吸附的主要原因,沥青质分子之间的氢键和π π作用使得沥青质构成超分子结构,此超分子结构将水分子包围在内,阻止了水滴的聚并。此外,模拟研究了一种化学破乳剂的破乳过程,结果发现,破乳剂可以通过沥青质分子的间隙,为后续的破乳过程提供了可能。     

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。     

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.     

沥青质组分轻质化转化的分子结构基础探索

渣油资源高效轻质化转化为轻、中质馏分原料,化工轻油,甚至直接产化学品,是提高渣油资源利用率的重要途径。渣油及沥青质组分的轻质化转化,实质是要大幅降低渣油的馏程范围使其从重变轻,以及降低沥青质沉淀析出倾向使体系相容性提高。研究发现,降芳环反应无论是对降低原料分子的沸点还是对减少原料分子的聚集倾向都具有显著正向效果。基于此,对沥青质组分的多环芳烃体系开展分子表征。结果表明：所研究的减压渣油沥青质分子以孤岛型结构为主,含有多个噻吩环且噻吩环主要处在分子结构内部位置,而噻吩环位于结构外围位置及湾型的含硫沥青质分子相对较少。基于分子表征结果探讨比较不同结构类型沥青质分子的降芳环反应路径,提出具有桥键或内部杂环的沥青质分子(群岛型Ⅰ、群岛型Ⅱ、群岛型Ⅲ和孤岛型Ⅰ)通过断桥键及加氢脱内部杂环反应可大幅度降低芳环数,从而显著降低沸点和聚集活性,实现轻质化目标,并且需要的氢耗较低。     

THE COLLOIDAL STRUCTURE OF CRUDE OILS AND SUSPENSIONS OF ASPHALTENES AND RESINS

ABSTRACT

A better understanding of colloidal macrostructure of the heavy petroleum products and their complex fractions is of great importance in the context of industrial problems that arise during the crude oil production, refining and transport. Much effort has been devoted to the chemical structure studies, but there is a need for more precise data regarding parameters that characterize those complex systems. For instance, the molecular weight of heavy molecules, the composition and size of aggregates formed during the industrial processing and their evolution upon the variation of temperature, pressure and with the addition of solvent have not been well known. In this paper we present new results obtained using several powerful techniques. Scattering methods (using X-rays and neutrons) are applied to study both the fractionated products (asphaltene and resin solutions in more or less good solvents) and the real systems (Safaniya vacuum residue). The lamellar structural model for asphaltenes and resins is confirmed and the molecular weight of these species determined using a polydisperse size distribution. Discussion is presented concerning the specificity of X-ray and neutron scattering : X-ray experiments are more sensitive to the aromatic-rich regions, whereas the neutron scattering data provide information about all the particle volume. Viscosimetry measurements provide information on the molecular shape of asphaltene and confirm the disk-like model. Critical micellar concentration has been obtained using Vapour Pressure Osmometry (VPO) for asphaltene suspensions in toluene and in pyridine. The resin molecules are smaller than asphaltenes, and appear to be a good solvent for asphaltenes. One of the major conclusions of this work is the wide-spread presence of density heterogeneities in diluted solutions of asphaltenes and resins as well as in the pure product (Safaniya vacuum residue). This was deduced from the scattering experiments and cryo-scanning electron microscopy data. The heating effects. were studied: a temperature increase leads to the decrease of molecular weight, but heterogeneities remain present. The structure of vacuum residue exhibits large density fluctuations which are thermally stable. These dense regions remain connected into a network up to 393°K and determine the yield value of the rheological behaviour.     

THE COLLOIDAL STRUCTURE OF CRUDE OILS AND SUSPENSIONS OF ASPHALTENES AND RESINS

A better understanding of colloidal macrostructure of the heavy petroleum products and their complex fractions is of great importance in the context of industrial problems that arise during the crude oil production, refining and transport. Much effort has been devoted to the chemical structure studies, but there is a need for more precise data regarding parameters that characterize those complex systems. For instance, the molecular weight of heavy molecules, the composition and size of aggregates formed during the industrial processing and their evolution upon the variation of temperature, pressure and with the addition of solvent have not been well known. In this paper we present new results obtained using several powerful techniques. Scattering methods (using X-rays and neutrons) are applied to study both the fractionated products (asphaltene and resin solutions in more or less good solvents) and the real systems (Safaniya vacuum residue). The lamellar structural model for asphaltenes and resins is confirmed and the molecular weight of these species determined using a polydisperse size distribution. Discussion is presented concerning the specificity of X-ray and neutron scattering : X-ray experiments are more sensitive to the aromatic-rich regions, whereas the neutron scattering data provide information about all the particle volume. Viscosimetry measurements provide information on the molecular shape of asphaltene and confirm the disk-like model. Critical micellar concentration has been obtained using Vapour Pressure Osmometry (VPO) for asphaltene suspensions in toluene and in pyridine. The resin molecules are smaller than asphaltenes, and appear to be a good solvent for asphaltenes. One of the major conclusions of this work is the wide-spread presence of density heterogeneities in diluted solutions of asphaltenes and resins as well as in the pure product (Safaniya vacuum residue). This was deduced from the scattering experiments and cryo-scanning electron microscopy data. The heating effects. were studied: a temperature increase leads to the decrease of molecular weight, but heterogeneities remain present. The structure of vacuum residue exhibits large density fluctuations which are thermally stable. These dense regions remain connected into a network up to 393°K and determine the yield value of the rheological behaviour.     

The Solubility and Three-Dimensional Structure of Asphaltenes

The tendency of the asphaltenes to form aggregates in hydrocarbon solution is one of their most characteristic features and has tended to complicate the determination of the structure of petroleum In addition, if the composition and properties of the precipitated asphaltenes reflect those of the micelles in solution, the latter should be considered as mixed micelles. This is a reasonable assumption in view of the large quantities of soluble resins found in the precipitated solid

Empirical observations indicate that the resins play an important role in stabilizing asphaltenes in crude oil and under unfavorable solvent conditions the asphaltene species are prone to further aggregation into clusters that are unstable and precipitate from the crude oil. It is also suggested that the resins and the asphaltenes from a particular crude oil have points of structural similarity relative to the asphaltenes and resins from another crude oil. On a more localized scale, i.e. in one particular crude oil there are also structural differences within the constituents of asphaltenes and structural differences within the constituents of the resins are also anticipated

Therefore, the structure of the micelles within any one crude oil must be expected to be varied and non-homogenous. From the evidence cited herein, it follows that the potential for graphite-type stacking by the asphaltene molecules in the center of a micelle might not be as great as the potential for the micelles forming by asphaltene-resin interactions rather than by asphaltene-asphaltene interactions