Asphaltenes: Fundamental Principles to Oilfield Applications

O. Mullins, A. Pomerantz, Yunlong Zhang
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Abstract

The sophisticated molecular imaging methods, atomic force microscopy (AFM) and scanning tunneling microscopy (STM), have been utilized to image individual asphaltene molecules, both their atoms and bonds, and their electronic structure. The stunning images have confirmed previous results and have all but resolved the long-standing uncertainties regarding asphaltene molecular architecture. Asphaltenes are also known to have a strong propensity to aggregate. The dominante asphaltene molecular structure and hierarchical nanocolloidal structures have been resolved and codified in the Yen-Mullins model. Use of this model in a simple polymer solution theory has given the first equation of state (EoS) for asphaltene gradients in oilfield reservoirs, the Flory-Huggins-Zuo EoS. With this EoS it is now possible to address reservoir connectivity in new ways; equilibrated asphaltenes imply reservoir connectivity. For reservoirs with disequilibrium of contained fluids, there is often a fluid process occurring in geologic time that precludes equilibrium. The collection of processes leading to equilibrium and those that preclude equilibrium constitute a new technical discipline, reservoir fluid geodynamics (RFG). Several reservoirs are reviewed employing RFG evaluation of connectivity via asphaltene thermodynamics. RFG processes in reservoris often include diffusion, RFG models incorporating simple solution to the diffusion equation coupled with quasi-equilibrium with the FHZ EoS are shown to apply for timelines up to 50 million years, the age of charge in a reservoir. When gas (or condensates) diffuse into oil, the asphaltenes are destabilized and can convect to the base of the reservoir. Increasing asphaltene onset pressure as well as viscous oil and tar mats can be consequences. Depending on specifics of the process, either gooey tar or coal-like asphaltene deposits can form. In addition, the asphaltene structures illuminated by AFM are now being used to account for interfacial properties using simple thermodynamics. At long last, asphaltenes are no longer the enigmatic component of crude oil, instead the resolution of asphaltene structures and dynamics has led to new thermodynamic applications in reservoirs, the new discipline RFG, and a new understanding of tar mats.
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沥青质:油田应用的基本原理
复杂的分子成像方法,原子力显微镜(AFM)和扫描隧道显微镜(STM),已经被用来成像单个沥青质分子,包括它们的原子和键,以及它们的电子结构。这些令人惊叹的图像证实了之前的结果,几乎解决了长期以来关于沥青质分子结构的不确定性。沥青质也有很强的聚集倾向。在Yen-Mullins模型中,主要的沥青质分子结构和分层的纳米胶体结构已经被分解和编码。将该模型应用于简单聚合物溶液理论,得到了油田储层沥青质梯度的第一个状态方程(EoS),即Flory-Huggins-Zuo EoS。有了这种EoS,现在可以用新的方式解决储层连通性问题;平衡沥青质意味着储层连通性。对于含有不平衡流体的储层,通常在地质时期发生的流体过程会排除平衡。导致平衡和那些阻止平衡的过程的集合构成了一门新的技术学科,即储层流体地球动力学。利用沥青质热力学对几个储层的连通性进行了RFG评价。储层中的RFG过程通常包括扩散,RFG模型将扩散方程的简单解与准平衡与FHZ EoS相结合,证明可适用于长达5000万年的时间线,即储层中的电荷年龄。当气体(或凝析油)扩散到石油中时,沥青质就会变得不稳定,并会对流到储层底部。随之而来的后果是沥青质起始压力的增加,以及油和焦油垫的粘稠。根据过程的具体情况,可以形成粘稠的焦油或类似煤的沥青质沉积物。此外,通过原子力显微镜观察到的沥青质结构现在也被用来解释简单热力学下的界面性质。最终,沥青质不再是原油中神秘的成分,相反,沥青质结构和动力学的解决导致了油藏中新的热力学应用,新的学科RFG,以及对焦油垫的新认识。
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