No abstract

The amount of energy in the form of natural gas hydrates is huge and likely substantially more than twice the amount of worldwide conventional fossil fuel. Various ways to produce these hydrates have been proposed over the latest five decades. Most of these hydrate production methods have been based on evaluation of hydrate stability limits rather than thermodynamic consideration and calculations. Typical examples are pressure reduction and thermal stimulation. In this work we discuss some of these proposed methods and use residual thermodynamics for all phases, including the hydrate phase, to evaluate free energy changes related to the changes in independent thermodynamic variables. Pressures, temperatures and composition of all relevant phases which participate in hydrate phase transitions are independent thermodynamic variables. Chemical potential and free energies are thermodynamic responses that determine whether the desired phase transitions are feasible or not. The associated heat needed is related to the first law of thermodynamics and enthalpies. It is argued that the pressure reduction method may not be feasible since the possible thermal gradients from the surroundings are basically low temperature heat that is unable to break water hydrogen bonds in the hydrate–water interface efficiently. Injecting carbon dioxide, on the other hand, leads to formation of new hydrate which generates excess heat compared to the enthalpy needed to dissociate the in situ CH4 hydrate. But the rapid formation of new CO2 hydrate that can block the pores, and also the low permeability of pure CO2 in aquifers, are motivations for adding N2. Optimum mole fractions of N2 based on thermodynamic considerations are discussed. On average, less than 30 mole% N2 can be efficient and feasible. Thermal stimulation using steam or hot water is not economically feasible. Adding massive amounts of methanol or other thermodynamic inhibitors is also technically efficient but far from economically feasible.

Hydrogenation of CO 2 is attractive to reduce CO 2 emissions and produce valueadded chemicals (e.g., methanol) with renewable energy. However, the mechanistic understanding of the role of water, a byproduct of CO 2 conversion to methanol, is still missing. Here, we identify that water directly participates in methanol formation via methoxy hydrolysis, and the enhancement on the water vapor diffusion strongly improves methanol selectivity and yield.