Kinetic Parameters for the Exchange of Hydrate Formers Last Reviewed 6/24/2014

FWP 65213

This project will investigate the kinetics associated with the production of natural gas from hydrate-bearing geologic media via unconventional technologies. The principal production technology of concern will be that of exchanging carbon dioxide (CO2) and nitrogen (N2) with clathrated methane (CH4).  The so-called guest-molecule exchange technology is attractive for its potential to maintain the geomechanical integrity of the reservoir formation as well as its carbon neutral potential.  As with other unconventional technologies, the ability of this technology to produce natural gas will depend both on our  understanding of and ability to exploit our knowledge of the processes. The research approach will be to understand the kinetic mechanisms that control the exchange of hydrate formers using numerical simulation to interpret field-scale trials, laboratory experiments to determine kinetic parameters, and code comparison to verify mathematical models and solution schemes.

Pacific Northwest National Laboratory (PNNL), Richland, Washington


Numerical Simulation
A new simulator in the STOMP simulator series for the production of natural gas hydrates from geologic accumulations has been developed and is currently being benchmarked. This new simulator, STOMP-HYDT-KE, is capable of modeling the production of natural gas hydrates via depressurization, thermal stimulation, inhibitor injection, and guest molecule exchange. The “HYDT” in the simulator name indicates the ternary hydrate system CH4-CO2-N2, and the “KE” indicates that the exchange of guest molecules and formation/dissociation of gas hydrates is modeled as a kinetic process. A major difficulty in developing STOMP-HYDT-KE was devising an equation of state that was reasonably accurate, computationally efficient, and free of convergence failures. The CH4-CO2-N2 system is particularly difficult to resolve in the hydrate stability region, as the mixture is often near its critical point. A hybrid tabular-cubic equation of state was developed that overcame convergence issues associated with pure cubic equations of state near the mixture critical point. The hybrid scheme uses tabular data and an innovative interpolation algorithm to establish the existing phases, gas molar fractions, and phase compositions. The cubic equation of state is then used to calculate phase densities and fugacity coefficients. STOMP-HYDT-KE is currently being benchmarked and has been successfully applied to an experiment conducted at the Korea Institute for Geoscience and Mineral Resources involving the injection of a CO2-N2 mixture into a CH4 hydrate-bearing, unsaturated column of sand.

Important issues regarding reservoir stimulation techniques, safety, and cost must be addressed before large-scale commercial recovery of natural gas from hydrates can be attempted. Reservoir modeling is an important tool for addressing these issues; however, applying this modeling tool requires access to reliable thermodynamic, kinetic, and physical property data for gas hydrates and physicochemical properties of the hydrate-bearing sediments themselves. Laboratory studies to characterize gas chemistries of synthetic gas hydrate sands have been conducted using a residual gas analyzer. The proposed experiments will leverage the results of previous experiments where the gas composition within a synthetically rich methane hydrate core was successfully monitored, allowing the use of acquired hydrate dissociation kinetics. Furthermore, proposed measurements using the pressurized x-ray diffraction technique are unique and will be some of the first reported. This technique was successfully used to track mineral dissolution, carbonation reactions, and mineral volume changes. The types of structural information gained from this technique are believed to improve fundamental understanding of mechanisms that occur during the gas swapping process.

Potential Impact

Numerical Simulation
The conventional technologies for producing natural gas hydrates from geologic repositories—especially those with pore-filling type hydrates—are reasonably well understood, and numerical simulations have been compared against field trials (Kurihara et al. 2008). In contrast, the guest-molecule-exchange approach for natural gas hydrate production is emerging unconventional technology. Laboratory-scale experiments by ConocoPhillips and researchers at the University of Bergen, Norway have demonstrated the exchange of CO2 with clathrated CH4, but there have only been a limited number of numerical simulation investigations of the technology. This project provides an opportunity for a recently developed numerical simulator, STOMP-HYDT-KE, to be used to aid in the interpretation of data collected from the 2012 Ignik Sikumi gas hydrate field trial. The ultimate objective of this field of research is to develop numerical simulation tools capable of predicting the performance of the guest-molecule-exchange technology at the reservoir scale, including the geomechanical stability of the process. The work represents a first step in validating a numerical simulator capable of modeling the kinetic exchange of hydrate guest molecules. A credible interpretation of the Ignik Sikumi gas hydrate field trial, realized through numerical simulation, will greatly increase understanding of the fundamental exchange processes for hydrate formers.

The goal of this experimental work is to conduct measurements of methane hydrate dissociation and structural stability in hydrate-bearing sediments using a high-pressure cell and state-of-the-art analytical techniques. The kinetic exchange rates obtained on the ternary gas system will be utilized to validate numerical codes and the structural data will further support the concept of continuous stability of gas hydrate structures during gas swapping.


Numerical Simulation
At the start of this project, the STOMP-HYDT-KE simulator was nearing the end of its development stage and had been demonstrated against laboratory-scale experiments conducted at the Korea Institute for Geosciences and Mineral Resources. The simulator, however, had not been applied beyond that verification exercise. Project personnel initially reviewed the numerical solution scheme and algorithms of the STOMP-HYDT-KE simulator. This review prompted a moderate redesign of the phase conditions, flash algorithms, boundary conditions, initial conditions and sources. The phase conditions were collapsed to four core conditions with options within each core condition: (1) aqueous saturated without hydrate, (2) aqueous unsaturated without hydrate, (3) aqueous unsaturated with hydrate, and (4) aqueous saturated with hydrate. The boundary conditions were collapsed to energy and flow types, and the number of initial condition variable options was reduced. All of the elements of the code redesign have been implemented and verified for proper execution.

Current Status (June 2014)

Numerical Simulation
The STOMP-HYDT-KE simulator is currently being applied to the Iġnik Sikumi field trial with the objective of using numerical simulation to interpret the collected data from the field trial.  Simulations were conducted over three periods of the field trial: (1) injection, (2) soak, and (3) production. This simulation work has been documented in two papers: (1) White, M.D. and W.S. Lee. 2014. “Guest molecule exchange kinetics for the 2012 Iġnik Sikumi Gas Hydrate Field Trial,” Proceedings of the Offshore Technology Conference held in Houston, Texas, USA, 5-8 May 2014, OTC-25374-MS., and (2) Anderson, B., R. Boswell, T. S. Collett, H. Farrell, S. Ohtsuka, and M. White. 2014. “Review of the findings of the Iġnik Sikumi CO2-CH4 gas hydrate exchange field trial,” Proceedings of the 8th International Conference on Gas Hydrates (ICGH8-2014),Beijing, China, from July 28 to August 1, 2014. Numerical simulation of the injection period of the Iġnik Sikumi #1 field trial revealed three important processes: (1) the guest molecule exchange process alters the equilibrium state for the hydrate, which can lead to hydrate dissociation or secondary hydrate formation; (2)  the guest molecule exchange process additionally alters the density of the hydrate, which can change the effective exchange process from being a  one-to-one molar exchange; and (3) the concept of bound-water is critical for preventing secondary hydrate from forming and clogging the pore space.  Comparison of the numerical simulations against the data collected during the injection period of the Iġnik Sikumi #1 field trial is not sufficient to uniquely determine the kinetic rate parameters for hydrate formation, dissociation, or guest-molecule exchange, as agreement between the gas injection rates between the field trial and numerical simulations can be made with different kinetic parameters by moderate alterations in scaling of the reservoir intrinsic permeabilities.

Project Start: June 1, 2013
Project End: December 31, 2015

Project Cost Information:
All DOE Funding
FY13 DOE Share: $90,000

FY14 DOE Share: $80,000

Total Funding to Date: $170,000 

Contact Information
NETL – John Terneus ( or 304-285-4254)
PNNL – Mark White ( or 509-372-6070)

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