Chen Zihui, Liu Bo, Manica Rogerio, Liu Qingxia, Xu Zhenghe
Department of Chemical and Materials Engineering, University of Alberta, Edmonton T6G 1H9, Canada.
Langmuir. 2020 Mar 3;36(8):2063-2070. doi: 10.1021/acs.langmuir.9b03887. Epub 2020 Feb 18.
The presence of immiscible water drops in bulk hydrocarbon is likely to bridge hydrate particles to cause hydrate agglomeration, leading to potential pipeline blockage. This can become a major challenge for flow assurance in offshore petroleum transportation. To avoid hydrate aggregation, the attachment between hydrate and water drops should be avoided. In this study, we used our home-designed integrated thin film drainage apparatus to investigate the interactions between a hydrate particle and a water drop inside model oil (i.e., mixture of cyclopentane and toluene with a volumetric ratio of 1:1). Our experiments showed that asphaltenes, a natural component in crude oil, were an effective inhibitor for the attachment between water drops and hydrate particles. Without asphaltenes in the system, the water drop adhered to the hydrate particle immediately after the two surfaces contacted. By adding 0.03 g/L asphaltenes into the oil phase, the attachment was delayed by 0.7 s when the applied preload force was set to around 0.05 mN. By increasing the asphaltenes addition to 0.05 g/L, the attachment between the hydrate and water drop was prevented even when the contact time lasted up to 25 s. This phenomenon could be explained by the adsorption of an asphaltenes layer along the interface between the aqueous drop and hydrocarbon. Measurements of the dynamic interfacial tension and crumping ratio confirmed the presence of the adsorption layer. The addition of 0.6 mol/L NaCl or 0.3 mol/L CaCl in the aqueous drop could further enhance the strength of the adsorption layer. Results of this research provide understanding of the benefits of asphaltenes and salt in preventing hydrate agglomeration.
在散装烃中存在不混溶的水滴可能会使水合物颗粒桥连,导致水合物团聚,从而可能造成管道堵塞。这可能成为海上石油运输中流动保障的一个重大挑战。为避免水合物聚集,应避免水合物与水滴之间的附着。在本研究中,我们使用自行设计的集成薄膜排水装置,研究了水合物颗粒与模型油(即体积比为1:1的环戊烷和甲苯的混合物)中的水滴之间的相互作用。我们的实验表明,原油中的天然成分沥青质是水滴与水合物颗粒之间附着的有效抑制剂。在系统中没有沥青质的情况下,两个表面接触后水滴立即附着在水合物颗粒上。当施加的预加载力设定为约0.05 mN时,通过向油相中添加0.03 g/L沥青质,附着延迟了0.7 s。通过将沥青质添加量增加到0.05 g/L,即使接触时间长达25 s,水合物与水滴之间的附着也能被阻止。这种现象可以通过沿水滴与烃之间的界面吸附一层沥青质来解释。动态界面张力和皱缩率的测量证实了吸附层的存在。在水滴中添加0.6 mol/L NaCl或0.3 mol/L CaCl可以进一步增强吸附层的强度。本研究结果有助于理解沥青质和盐在防止水合物团聚方面的作用。