Journal of Chemical and Engineering Data, Vol.63, No.3, 832-844, 2018
Alternative Routes to Hydrate Formation during Processing and Transport of Natural Gas with a Significant Amount of CO2: Sleipner Gas as a Case Study
Carbon dioxide from the Sleipner gas field in the North Sea has now been injected into the Utsira Formation for more than 20 years. A million tons of carbon dioxide per year is transported and injected. Conditions of temperatures and pressures in the injection pipeline as well as inside the reservoir are outside hydrate-forming conditions. Transport pipelines, on the other hand, are subject to low temperatures and high pressures, which can potentially lead to hydrate formation. In this work, we examine some possible routes to hydrate formation and the consequences for maximum amounts of water that can be permitted to follow the gas. A conventional hydrate risk evaluation involves calculation of water dew point concentrations in the gas as an upper tolerance limit for preventing liquid water to drop out from the gas and eventually form hydrates. Pipelines are rusty even from the moment they are placed on the seafloor in the North Sea. Initially this rust consists of various forms of iron oxides. Hematite (Fe2O3) is one of the most stable of these and is used as a model for rust in this work. A second route to hydrate formation involves adsorption of water on rusty surfaces. Earlier work in the open literature indicates that the chemical potential of adsorbed water may be substantially lower than the chemical potential of liquid water at the same temperature and pressure. This opens up a path for heterogeneous hydrate nucleation toward the pipeline walls. The chemical potential of the first few adsorbed water layers (roughly 1 nm) is too low for them to form hydrates, but outside of that the liquid structure is similar to that of liquid water and can form hydrates. The estimated maximum water content that can be permitted on the basis of the water dew point was found to be on the order of 20 times higher than the amount that would be tolerated if adsorption on hematite were the tolerance criterion. This ratio is similar for the original Sleipner gas with carbon dioxide and the hydrocarbon phase after separation of the carbon dioxide. As expected, the difference is not substantial in absolute tolerance given that the carbon carbon dioxide content is less than 3.5 mol %. Another aspect is the possibility of forming more than one type of hydrate. The dominating components in the mixture are methane, ethane, and carbon dioxide, which are structure I formers. The presence of 3 mol % propane and 0.25 mol % isobutane will have a substantial impact on the dew point curve and thus also the whole phase envelope of the system. The solubility of water in condensed hydrocarbon is qualitatively different and increases with pressure, in contrast to the solubility in supercritical methane. However, the relative tolerance limits between the dew point criterion and the adsorption criterion is found to be on the same order of magnitude as for the gas mixture. The pipeline walls are typically the coldest regions of the pipeline and rarely exceed 280 K for the North Sea seafloor. Sensitivity analyses of the maximum tolerance for water as a function of propane content in methane and in carbon dioxide are also conducted and confirm the relative tolerance limits.