Energy Conversion and Management, Vol.48, No.1, 242-250, 2007
Thermodynamic simulations of hydrate formation from gas mixtures in batch operations
This paper deals with the hydrate formation from mixed hydrate-forming gases such as natural gas to be converted to hydrates for the purpose of its storage and biogases from which carbon dioxide is to be separated by hydrate formation. When a batch operation is selected for processing such a gas mixture in a closed reactor, we need to predict the evolution of the thermodynamic and compositional states inside the reactor during the operation. We have contrived a simulation scheme that allows us to estimate the simultaneous changes in the composition of the residual gas, the structure of the hydrate formed and the guest composition in the hydrate, in addition to the change in the system pressure, with the progress of hydrate formation during each operation. This scheme assumes the transient hydrate forming process in a reactor during each operation to be a series of numerous equilibrium states, each slightly deviating from the preceding state. That is, a thermodynamic system composed of the contents of the reactor is assumed to be subjected to a quasi-static, irreversible change in state, instantaneously keeping itself in thermodynamic equilibrium. The paper demonstrates a simulation of a process of hydrate formation from a methane + propane mixture and compares its results to relevant experimental results reported by Uchida et al. [Uchida T, Morikawa M, Takeya S, Ikeda IY, Ohmura R, Nagao J, et al. Two-step formation of methane-propane mixed gas hydrates in a batch-type reactor. AIChE J 2004;50(2):518-23]. (c) 2006 Elsevier Ltd. All rights reserved.
Keywords:mixed hydrate;natural gas hydrate;thermodynamic simulation;gas separation;hydrate-based technology