Black Sea hydrate production value and options for clean energy production

Natural gas hydrates of Bulgaria and Romania in the Black Sea have been subject to studies by several European research projects. The current understanding of the hydrate distribution, and the total amounts of hydrate in the region, makes it interesting to evaluate in terms of commercial potential. In this study, we have evaluated some well-known hydrate production methods. Thermal stimulation and adding chemicals are considered as not economically feasible. Pressure reduction may not be efficient due to the endothermic dissociation of hydrates and long-term cooling of the sediments. Chemical work due to pressure reduction is an additional mechanism but is too slow to be commercially feasible. Adding CO₂/N₂, however, has a dual value. In the future, CO₂ can be stored at a price proportional to a CO₂ tax. This is deducted from the value of the released natural gas. The maximum addition of N₂ is around 30 mol% of the CO₂/N₂ mixture. A minor addition (in the order of 1 mol%) of CH₄ increases the stability of the hydrate created from the injection gas. The maximum N₂ amount is dictated by the demand for the creation of a new hydrate from injection gas but also the need for sufficient heat release from this hydrate formation to dissociate the in situ CH₄ hydrates. An additional additive is needed to accelerate the formation of hydrate from injection gas while at the same time reducing the creation of blocking hydrate films. Based on reasonable assumptions and approximations as used in a verified kinetic model it is found that CH₄/CO₂ swapping is a feasible method for Black Sea hydrates. It is also argued that the technology is essentially conventional petroleum technology combined with learning from projects on aquifer storage of CO₂, and a thermodynamic approach for design of appropriate injection gas. It is also argued that the CH₄/CO₂ swap can be combined with well-known technology for steam cracking of produced hydrocarbons to H₂ and CO₂ (for re-injection).