The effects of porous medium heterogeneity on methane hydrate formation, water flow through the heterogeneous hydrate-bearing sand, and hydrate dissociation were observed in an experiment using a heterogeneous sand column with prescribed heterogeneities. X-ray computed tomography (CT) was used to monitor saturation changes in water, gas, and hydrate during hydrate formation, water flow, and hydrate dissociation. The sand column was packed in several segments having vertical and horizontal layers with two distinct grain-size sands. The CT images showed that as hydrate formed, the water and hydrate saturations were dynamically redistributed by variations in capillary strength of the medium (the tendency for a material to imbibe water), which changed with the presence and saturation of hydrate. Water preferentially flowed through fine sand near higher hydrate-saturation regions where the capillary strength was elevated relative to the lower hydrate saturation regions. Hydrate dissociation initiated by depressurization varied with different grain sizes and hydrate saturations.

It is well known that water molecules at room temperature tend to form ‘iceberg’ structures around the hydrocarbon chains of surfactant molecules dissolved in water. The entropy reduction (times the absolute temperature T) associated with the iceberg structure can be considered as the net driving force for self-assembly. More recently, many investigators measured long-range attractive forces between hydrophobic surfaces, which are likely to result from structuring of the water molecules in the vicinity of the hydrophobic surfaces. Similarly, the hydrophobic nature of most gas hydrate formers may induce ordering of water molecules in the vicinity of dissolved solutes. In the present work, the surface forces between thiolated gold surfaces have been measured using an atomic force microscope (AFM) to obtain information on the structure of the thin films of water between hydrophobic surfaces. The results have been used to develop a new concept for the formation of gas hydrates.

Pressure drawdown tests were conducted using Schlumberger’s Modular Formation Dynamics Tester™ (MDT) wireline tool in the Mallik methane hydrate (MH) reservoirs in February 2002 as well as in the Mount Elbert (Alaska) MH reservoirs in February 2007, while a production test was conducted applying a depressurization method in one of the Mallik MH reservoirs in April 2007. All of these tests aimed at measuring production and bottomhole pressure (BHP) responses by reducing BHP below the MH stability pressure to estimate reservoir properties such as permeability and MH dissociation radius. We attempted to analyze the results of these tests through history matching using the numerical simulator (MH21-HYDRES) coded especially for gas hydrate reservoirs. Although the magnitude of depressurization and the total duration spent for these tests were almost identical to each other, the simulation studies revealed that there existed significant differences in what could be inferred and could not be inferred from test results between a MDT test and a production test. The simulation studies mainly clarified that (1) the MDT tests were useful to estimate initial effective permeability in the presence of MH, (2) when BHP is reduced below the MH stability pressure at MDT tests, the pressure and temperature responses were significantly influenced by the wellbore storage erasing all the important data such as those indicating a radius of MH dissociation and effective permeability after partial MH dissociation, and (3) history matching of production tests tended to result in multiple solutions unless establishing steady flow conditions. This paper presents the results of history matching for the typical MDT and production tests conducted in Mallik and Alaska MH reservoirs. This paper also discusses the parameters reliably estimated through MDT and production tests, which should provide many suggestions on future designs and analyses of short-term tests for MH reservoirs.

A gas hydrate production test using the depressurization method was conducted in early April 2007 as part of the JOGMEC/NRCan/Aurora Mallik production research program. The results of the production test were analyzed using a numerical simulator (MH21-HYDRES) coded especially for gas hydrate reservoirs. This paper evaluates the test results based on analyses of production test data, numerical modeling and a series of history matching simulations. Methane gas and water was produced from a 12 m perforation interval within one of the major methane hydrate (MH) reservoirs at the Mallik MH field, by reducing the bottomhole pressure down to about 7 MPa. The measured gas production rate was far higher than that expected for a comparatively small pressure drawdown. However, irregular (on-off) pumping operations, probably related to excessive sand production, resulted in unstable fluid flow within the wellbore, which made the analysis of test performance extremely complicated. A numerical reservoir model was constructed as a series of grid blocks, including those mimicking the wellbore, to enable rigorous simulation of fluid flow patterns in the vicinity of the wellbore. The model was then tuned through history matching, not by simply adjusting reservoir parameters, but by introducing the concept that sand production might have dramatically increased the near-wellbore permeability. The good agreement between observed and simulated performances suggests the mechanism of MH dissociation/production during the test. The history matched reservoir model was employed to predict the second-year production test performance, in order to examine the gas production potential of the Mallik MH reservoir, and to provide insight into future exploration and development planning for MH reservoirs.

Design and construction of long term gas hydrate production facilities will require assessment of the in situ formation response to production at a field scale. Key parameters such as temperature and pressure are critical for the determination of phase conditions, others such as formation resistivity, formation acoustic properties and fluid mobility support the inference of gas hydrate saturation, permeability and porosity. An ability to continuously monitor the response of these parameters during the course of a production test would facilitate tracking of the dissociation front and yield valuable information for engineering design and verification of numerical reservoir simulators. Such a monitoring system has been designed, developed and introduced as a part of the Japan Oil, Gas and Metals National Corporation and Natural Resources Canada gas hydrate production testing program carried out in the winter of 2007 in the Mackenzie Delta, Canada. While the deployment of some sensors and the acquisition of some data sets were limited due to operational problems encountered during the field program, considerable experience has been gained during all phases of the research program. In particular, the acquisition and interpretation of downhole temperature profiles and changes in formation electrical potentials during testing provide insight into the production response of the reservoir and may assist in the understanding of operational conditions and related decision-making processes.

The purpose of this study is to develop the production method of CO2 hydrate-slurry. In this paper, the production process of CO2 hydrates with pure water dissolved antifreeze proteins (AFPs) is discussed. CO2 hydrate-slurry can be transported from a production place to storage one with a small pressure loss. The AFPs have made the hydrate particles be small and well disperse. It is revealed that the Type III AFPs are effective for the inhibition of structure I hydrate production. By the present experiments, the induction time for the hydrate production increases, and moreover the formation rate of the hydrate and the increasing rate of an agitator torque decrease.

This work is part of a research project sponsored by the Italian Electricity Agency for CO2 disposal in form of hydrate. The dissociation behavior of CH4 hydrate was taken as a reference for the study of the CO2 hydrate preservation. The formation and dissociation of CO2 and CO2–THF mixed hydrates, compared to CH4 and CH4 – THF mixed hydrates, has been considered. The experimental tests were performed in a 2 liter reaction calorimeter at pressures between 0.1 and 0.3 MPa. The dissociation has been followed at temperatures from -3 °C to 0 °C for CO2 and CH4 hydrates, and from -3 °C to 10 °C for THF mixed hydrates. More than pressure, which is very important for methane hydrates, temperature affects the preservation of CO2 and CO2–THF mixed hydrates. Subcooling after formation is important for methane hydrate preservation, but it does not substantially affect CO2 hydrate stability. In the studied P, T range, CO2 hydrate does not present any anomalous self-preservation effect. The mixtures containing more ice show a slower dissociation rate. Methane hydrate requires less energy to dissociate than CO2 hydrate and, therefore, is less stable. On the contrary, the mixed CO2 – THF hydrates are less stable than the mixed methane hydrates. Modulated differential scanning calorimetry (MDSC) has been used for hydrate characterization: both CH4 and CO2 hydrates include two decomposition peaks, the first due to the melting of the ice and the second to the decomposition of the hydrate. The higher temperature of the decomposition peak of CO2 hydrate confirms its higher stability respect to CH4 hydrate.

Depressurization is thought to be a promising method for gas recovery from methane hydrate reservoirs, but considerable water production is expected when this method is applied to the hydrate reservoir of high initial water saturation. In this case, the prediction of water production is a critical problem. This study examined relative permeability curves during hydrate dissociation by comparing numerical simulations with laboratory experiments. Data of gas and water volumes produced during depressurization were taken from gas recovery experiments using sand-packed cores containing methane hydrates. In each experiment, hydrates were dissociated by depressurization at a constant pressure. The surrounding temperature was held constant during dissociation. The volumes of gas and water produced, the temperatures inside of the core, and the pressures at the both ends of the core were measured continuously. The experimental results were compared with numerical simulations by using the simulator MH21-HYDRES (MH21 Hydrate Reservoir Simulator). The experimental results showed that considerable volume of water was produced during hydrate dissociation, and the simulator could not reproduce the large water production when we used typical relative permeability curves such as the Corey model. To obtain good matching for the volumes of gas and water produced during hydrate dissociation, the shape of relative permeability curves was modified to express the rapid decrease in gas permeability with increasing water saturation. This result suggests that the connate water can be easily displaced by hydrate-dissociated gas and move forward in the hydrate reservoir of high initial water saturation.

Understanding the formation conditions of seep carbonate is crucial to better constrain the dynamic fluid flow and chemical fluxes associate with cold seeps on the seafloor. Rare earth element (REE) in seep carbonates collected from modern cold seeps of Gulf of Mexico, Black Sea, Congo Fan, ancient seeps of Beauvoisin (Oxfordian, J3, Southeastern France) and Marmorito (Miocene, Northern Italy) were studied. Our focus has been on 5% HNO3-treated solution (authigenic carbonate minerals) of carbonates. Several crystalline forms of carbonate minerals have been selected for analysis. Total REE (ΣREE) contents in seep carbonates varies widely, from 0.068 to 43.655 ppm, but the common trend is that the ΣREE in microcrystalline phases is highest and lowest of in sparite, suggesting that the ΣREE of seep carbonates may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates show varied Ce anomalies across several seep sites and even within one site, suggesting that the formation condition of seep carbonate is variable and complex. Overall, our results show that apart from anoxic, oxic formation condition is also common at hydrocarbon seep environments.

Stable isotope of natural gas hydrates provides useful information of their gas sources. We investigated the isotopic fractionation of gas molecules during the formation of synthetic gas hydrates composed of methane and ethane. The gas hydrate samples were experimentally prepared in a pressure cell and isotopic compositions (δ13C and δD) of both residual and hydratebound gases were measured. δD of hydrate-bound molecules of methane and ethane hydrates was several per mil lower than that of residual gas molecules in the formation processes, while there was no difference in the case of δ13C. Effect of temperature on the isotopic fractionation was also investigated and it was found that the fractionation was effective at low temperature.