Blockage of pipelines due to hydrate formation is a major problem for subsea flow assurance. Induction time for hydrate formation from the multiphase system within a pipeline is a critical parameter to determine whether hydrates may form at a given time. In this work, the induction time for hydrate formation in water-in-oil emulsions was investigated under different conditions. For this purpose, an autoclave with an online viscometer was designed and built. Based on the viscosity variation observed in the experiments during hydrate formation, a new avenue for defining induction time is proposed, which should be more convenient for determining the hydrate formation time in some pipelines. As hydrate formation in emulsions is more complicated than in pure water, the effects of several factors were considered in this study, including water cut of the emulsions, shear rate, driving force, and memory effect. Additionally, wax precipitation is also a common problem in subsea pipelines and can impact flow assurance when hydrate formation and wax precipitation both occur. Consequently, the effect of wax solid particles on hydrate formation was also considered in this work. The presence of wax particles is observed to impede hydrate formation. In this work, it is determined from induction time that the hydrate formation is initiated at the water–oil surface for water-in-oil emulsion. Moreover, the memory effect can shorten induction times of hydrate formation due to the remaining small CO2 bubbles at the surface of water droplets.

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Here we fabricate a new type of flexible and versatile nanohybrid paper electrode by ultrasonic-electrodeposition of PtPd alloy nanoparticles on freestanding ionic liquid (IL)-functionalized graphene paper, and explore its multifunctional applications in electrochemical catalysis and sensing systems. The graphene-based paper materials demonstrate intrinsic flexibility, exceptional mechanical strength and high electrical conductivity, and therefore can serve as an ideal freestanding flexible electrode for electrochemical devices. Furthermore, the functionalization of graphene with IL (i.e., 1-butyl-3-methylimidazolium tetrafluoroborate) not only increases the electroactive surface area of a graphene-based nanohybrid paper electrode, but also improves the adhesion and dispersion of metal nanoparticles on the paper surface. These unique attributes, combined with the merits of an ultrasonic-electrodeposition method, lead to the formation of PtPd alloy nanoparticles on IL-graphene paper with high loading, uniform distribution, controlled morphology and favourable size. Consequently, the resultant nanohybrid paper electrode exhibits remarkable catalytic activity as well as excellent cycle stability and improved anti-poisoning ability towards electrooxidation of fuel molecules such as methanol and ethanol. Furthermore, for nonenzymatic electrochemical sensing of some specific biomarkers such as glucose and reactive oxygen species, the nanohybrid paper electrode shows high selectivity, sensitivity and biocompatibility in these bio-catalytic processes, and can be used for real-time tracking hydrogen peroxide secretion by living human cells. All these features demonstrate its promising application as a versatile nanohybrid electrode material in flexible and lightweight electrochemical energy conversion and biosensing systems such as bendable on-chip power sources, wearable/implantable detectors and in vivo micro-biosensors.

Hydrate formation and wax deposition pose great flow assurance challenges to subsea oil pipes, especially when the two phenomena co-occur. Wax crystals can have a significant impact on hydrate nucleation and growth kinetics, but this phenomenon has not been studied in great detail. Here, the effect of wax crystals on hydrate nucleation was investigated using both molecular dynamics simulation methods and experiments conducted using a custom-designed high-pressure autoclave equipped with an on-line viscometer. Both the simulation and the experimental results demonstrated that the presence of wax crystals inhibits hydrate nucleation. The simulations showed that water droplets tend to approach and adsorb on wax crystals prior to nucleation, thus inhibiting the formation of hydrate cages. The experiments demonstrated that water cut and stirring rate play a significant role in determining the hydrate nucleation rate. In addition, adding more wax increased the viscosity of the emulsion, which limits mass transfer of gas to the oil−water interface.

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