Bjørn Kvamme

Storage of CO2 in natural gas hydrate reservoirs and the effect of hydrate as an extra sealing in cold aquifers

Abstract Reservoirs of clathrate hydrates of natural gases (hydrates), found worldwide and containing huge amounts of bound natural gases (mostly methane), represent potentially vast and yet untapped energy resources. Since CO2-containing hydrates are considerably more stable thermodynamically than methane hydrates, if we find a way to replace the original hydrate-bound hydrocarbons by the CO2, two goals can be accomplished at the same time: safe storage of carbon dioxide in hydrate reservoirs, and in situ release of hydrocarbon gas. We have applied the techniques of Magnetic Resonance Imaging (MRI) as a tool to visualize the conversion of CH4 hydrate within Bentheim sandstone matrix into the CO2 hydrate. Corresponding model systems have been simulated using the Phase Field Theory approach. Our theoretical studies indicate that the kinetic behaviour of the systems closely resembles that of CO2 transport through an aqueous solution. We have interpreted this to mean that the hydrate and the matrix mineral surfaces are separated by liquid-containing channels. These channels will serve as escape routes for released natural gas, as well as distribution channels for injected CO2.

Using magnetic resonance imaging to monitor CH4 hydrate formation and spontaneous conversion of CH4 hydrate to CO2 hydrate in porous media

Magnetic resonance imaging was used to monitor and quantify methane hydrate formation and exchange in porous media. Conversion of methane hydrate to carbon dioxide hydrate, when exposed to liquid carbon dioxide at 8.27 MPa and approximately 4 degrees C, was experimentally demonstrated with MRI data and verified by mass balance calculations of consumed volumes of gases and liquids. No detectable dissociation of the hydrate was measured during the exchange process.

Methane clathrate hydrates: melting, supercooling and phase separation from molecular dynamics computer simulations

The melting of structure I methane clathrate hydrate has been investigated using NVT molecular dynamics simulations, for a number of potential energy models for water and methane. The equilibrated hydrate crystal has been heated carefully from 270 K, in steps of 5 K, until a well defined phase instability appears. At a density of 0⋅92 g cm-3, an upper bound for the mechanical stability of the methane hydrate lattice over a timescale of 11 nanoseconds is 330 K. Finite size effects have been investigated by simulating systems of 1 and 8 units cells of methane hydrate. The properties of the melted system upon cooling are examined.

Kinetics of solid hydrate formation by carbon dioxide: Phase field theory of hydrate nucleation and magnetic resonance imaging

In the course of developing a general kinetic model of hydrate formation/reaction that can be used to establish/optimize technologies for the exploitation of hydrate reservoirs, two aspects of CO2 hydrate formation have been studied. (i) We developed a phase field theory for describing the nucleation of CO2 hydrate in aqueous solutions. The accuracy of the model has been demonstrated on the hard-sphere model system, for which all information needed to calculate the height of the nucleation barrier is known accurately. It has been shown that the phase field theory is considerably more accurate than the sharp-interface droplet model of the classical nucleation theory. Starting from realistic estimates for the thermodynamic and interfacial properties, we have shown that under typical conditions of CO2 formation, the size of the critical fluctuations (nuclei) is comparable to the interface thickness, implying that the droplet model should be rather inaccurate. Indeed the phase field theory predicts considerably smaller height for the nucleation barrier than the classical approach. (ii) In order to provide accurate transformation rates to test the kinetic model under development, we applied magnetic resonance imaging to monitor hydrate phase transitions in porous media under realistic conditions. The mechanism of natural gas hydrate conversion to CO2-hydrate implies storage potential for CO2 in natural gas hydrate reservoirs, with the additional benefit of methane production. We present the transformation rates for the relevant processes (hydrate formation, dissociation and recovery).

MRI Visualization of Spontaneous Methane Production From Hydrates in Sandstone Core Plugs When Exposed to CO2

Magnetic resonance imaging (MRI) of core samples in laboratory experiments showed that CO2 storage in gas hydrates formed in porous rock resulted in the spontaneous production of methane with no associated water production. The exposure of methane hydrate in the pores to liquid CO2 resulted in methane production from the hydrate that suggested the exchange of methane molecules with CO2 molecules within the hydrate without the addition or subtraction of significant amounts of heat. Thermodynamic simulations based on Phase Field Theory were in agreement with these results and predicted similar methane production rates that were observed in several experiments. MRI-based 3D visualizations of the formation of hydrates in the porous rock and the methane production improved the interpretation of the experiments. The sequestration of an important greenhouse gas while simultaneously producing the freed natural gas offers access to the significant amounts of energy bound in natural gas hydrates and also offers an attractive potential for CO2 storage. The potential danger associated with catastrophic dissociation of hydrate structures in nature and the corresponding collapse of geological formations is reduced because of the increased thermodynamic stability of the CO2 hydrate relative to the natural gas hydrate.

Multiscale approach to CO2 hydrate formation in aqueous solution: Phase field theory and molecular dynamics. Nucleation and growth

A phase field theory with model parameters evaluated from atomistic simulations/experiments is applied to predict the nucleation and growth rates of solid CO(2) hydrate in aqueous solutions under conditions typical to underwater natural gas hydrate reservoirs. It is shown that under practical conditions a homogeneous nucleation of the hydrate phase can be ruled out. The growth rate of CO(2) hydrate dendrites has been determined from phase field simulations as a function of composition while using a physical interface thickness (0.85+/-0.07 nm) evaluated from molecular dynamics simulations. The growth rate extrapolated to realistic supersaturations is about three orders of magnitude larger than the respective experimental observation. A possible origin of the discrepancy is discussed. It is suggested that a kinetic barrier reflecting the difficulties in building the complex crystal structure is the most probable source of the deviations.

Phase field theory of crystal nucleation in hard sphere liquid

The phase field theory of crystal nucleation described in L. Granasy, T. Borzsonyi, and T. Pusztai, Phys. Rev. Lett. 88, 206105 (2002) is applied for nucleation in hard-sphere liquids. The exact thermodynamics from molecular dynamics is used. The interface thickness for phase field is evaluated from the cross-interfacial variation of the height of the singlet density peaks. The model parameters are fixed in equilibrium so that the free energy and thickness of the (111), (110), and (100) interfaces from molecular dynamics are recovered. The density profiles predicted without adjustable parameters are in a good agreement with the filtered densities from the simulations. Assuming spherical symmetry, we evaluate the height of the nucleation barrier and the Tolman length without adjustable parameters. The barrier heights calculated with the properties of the (111) and (110) interfaces envelope the Monte Carlo results, while those obtained with the average interface properties fall very close to the exact values. In contrast, the classical sharp interface model considerably underestimates the height of the nucleation barrier. We find that the Tolman length is positive for small clusters and decreases with increasing size, a trend consistent with computer simulations.

Thermodynamic properties and phase transtions in the H2O/CO2/CH4 system

The availability of free energy densities as functions of temperature, pressure and the composition of all components is required for the development of a three-component phase field theory for hydrate phase transitions. We have broadened the extended adsorption theory due to Kvamme and Tanaka (J. Phys. Chem., 1995, 99, 7114) through derivation of the free energy density surface in case of CO2 and CH4 hydrates. A combined free energy surface for the liquid phases has been obtained from a SRK equation of state and solubility measurements outside hydrate stability. The full thermodynamic model is shown to predict water–hydrate equilibrium properties in agreement with experiments. Molecular dynamics simulations of hydrates in contact with water at 200 bar and various temperatures allowed us to estimate hard-to-establish properties needed as input parameters for the practical applications of proposed theories. The 5–95 confidence interval for the interface thickness for the methane hydrate/liquid water is estimated to 8.54 A. With the additional information on the interface free energy, the phase field theory will contain no adjustable parameters. We provide a demonstration of how this theory can be applied to model the kinetics of hydrate phase transitions. The growth of hydrate from aqueous solution was found to be rate limited by mass transport, with the concentration of solute close to the hydrate approaching the value characterizing the equilibrium between the hydrate and the aqueous solution. The depth of the interface was estimated by means of the phase field analysis; its value is close to the interface thickness yielded by molecular simulations. The variation range of the concentration field was estimated to approximately 1/3 of the range of the phase field.

Thermodynamic properties and interfacial tension of a model water–carbon dioxide system

We performed molecular dynamics (MD) simulations of liquid–liquid and liquid–vapor interfaces between bulk water and carbon dioxide. Interfacial systems, constructed from periodically replicated slabs, were studied at different pressures and temperatures by means of npT and nVT MD. Constant-pressure runs of 3, 1.2, and 0.3 nanoseconds were used to estimate the water–CO2 interfacial tension at 284.5 K and 298 K for a liquid–liquid system comprising 108 SPC water molecules and 108 three-site CO2 molecules. The liquid–vapor interface was studied under nVT conditions using 108 water molecules and 32 CO2 molecules. Interfacial tension was obtained from the difference between pressure components normal and tangential to the interface. The results showed a surprisingly (CO2 potential used has been never optimized for water–CO2 interaction) good agreement with experimental data; our model system also reproduced the pressure–temperature relationship of the interfacial tension. A second liquid–liquid system of 256 SPC water and 108 CO2 molecules was tested for temperature persistence of the interface at higher pressures (100 atm and 300 atm). The results of the simulation prove the feasibility of using the model system to predict the key properties of liquid–liquid water–carbon dioxide interface under widely varying conditions, including those relevant for deep-sea disposal of carbon dioxide.

Molecular simulations as a tool for selection of kinetic hydrate inhibitors

Natural gas hydrates are ice-like structures in which water molecules form a cage around gas molecules. They have been a problem in the petroleum industry. The heavy cost of alcohol and glycol injections needed to suppress the formation of hydrates has spurred an interest in so-called “kinetic inhibitors”, able to slow down the hydrate formation rather than prevent it. An earlier work (Kvamme, B. et al. 1997, Mol. Phys., 90, p. 979) proposed a simulation-based scheme to assess the comparative performance of prospective inhibitors and select the best candidates for experimental testing. In this work, we employed molecular dynamics simulations to test several kinetic inhibitors in a multiphase water–hydrate system with rigid hydrate interface. In addition, a long-scale run was implemented for a system where the hydrate was free to melt and reform. Our conclusion that PVCap inhibitor will outperform PVP as a kinetic hydrate inhibitor is supported by experimental data. We demonstrate that numerical experiments can be a valuable tool for selecting kinetic inhibitors as well as provide insight into mechanisms of kinetic inhibition and hydrate melting and reformation.