ALBERT

Description: Microbial mats collected at cold methane seeps in the Black Sea carry out anaerobic oxidation of methane (AOM) to carbon dioxide using sulfate as the electron acceptor. These mats, which predominantly consist of sulfate-reducing bacteria and archaea of the ANME-1 and ANME-2 type, contain large amounts of proteins very similar to methyl-coenzyme M reductase from methanogenic archaea. Mass spectrometry of mat samples revealed the presence of two nickel-containing cofactors in comparable amounts, one with the same mass as coenzyme F430 from methanogens (m/z = 905) and one with a mass that is 46 Da higher (m/z = 951). The two cofactors were isolated and purified, and their constitution and absolute configuration were determined. The cofactor with m/z = 905 was proven to be identical to coenzyme F430 from methanogens. For the m/z = 951 species, high resolution ICP-MS pointed to F430 + CH2S as the molecular formula, and LA-ICP-SF MS finally confirmed the presence of one sulfur atom per nickel. Esterification gave two stereoisomeric pentamethyl esters with m/z = 1021, which could be purified by reverse phase HPLC and were subjected to comprehensive NMR analysis, allowing determination of their constitution and configuration as (172S)−172-methylthio-F430 pentamethyl ester and (172R)−172-methylthio-F430 pentamethyl ester. The corresponding diastereoisomeric pentaacids could also be separated by HPLC and were correlated to the esters via mild hydrolysis of the latter. Equilibration of the pentaacids under acid catalysis showed that the (172S) isomer is the naturally occurring albeit thermodynamically less stable one. The more stable (172R) isomer (80% at equilibrium) is an isolation artifact generated under the acidic conditions necessary for the isolation of the cofactors from the calcium carbonate-encrusted mats.

Description: Marine methane hydrate in sands has huge potential as an unconventional gas resource; however, no field test of their production potential had been conducted. Here, we report the world’s first offshore methane hydrate production test conducted at the eastern Nankai Trough and show key findings toward future commercial production. Geological analysis indicates that hydrate saturation reaches 80% and permeability in the presence of hydrate ranges from 0.01 to 10 mdarcies. Permeable (1–10 mdarcies) highly hydrate-saturated layers enable depressurization-induced gas production of approximately 20,000 Sm3/D with water of 200 m3/D. Numerical analysis reveals that the dissociation zone expands laterally 25 m at the front after 6 days. Gas rate is expected to increase with time, owing to the expansion of the dissociation zone. It is found that permeable highly hydrate-saturated layers increase the gas–water ratio of the production fluid. The identification of such layers is critically important to increase the energy efficiency and the technical feasibility of depressurization-induced gas production from hydrate reservoirs.

Description: The guest-exchange method (or replacement) for methane production from gas hydrates has recently received attention because it can be used for both carbon dioxide sequestration and methane production. The structure of gas hydrates is maintained as a structure I (sI) hydrate while methane molecules are exchanged with carbon dioxide. In this study, CH4 + CO2 mixed gas hydrates were examined under terahertz light at various temperatures to simulate CH4–CO2 exchange reactions. Each gas hydrate composition examined was a representative composition at each step of the exchange reaction. The molecular composition was also accurately analyzed by gas chromatography. Refractive indices calculated by the terahertz time-domain spectroscopy (THz-TDS) of gas hydrate samples were correlated to the guest composition, and this novel method was proven to be used to quantify the extent of replacement via optical constant. Furthermore, changes in the water framework from the sI hydrate to ice using THz-TDS were investigated with an increasing temperature. Overall, this study reveals the process of guest exchange and phase transition from a gas hydrate to ice via the optical properties in the terahertz region, and it offers a powerful tool in gas hydrate production.

Description: Microscopy, confocal Raman spectroscopy and powder X-ray diffraction (PXRD) were used for in situ investigations of the CO2-hydrocarbon exchange process in gas hydrates and its driving forces. The study comprises the exposure of simple structure I CH4 hydrate and mixed structure II CH4–C2H6 and CH4–C3H8 hydrates to gaseous CO2 as well as the reverse reaction, i.e., the conversion of CO2-rich structure I hydrate into structure II mixed hydrate. In the case of CH4–C3H8 hydrates, a conversion in the presence of gaseous CO2 from a supposedly more stable structure II hydrate to a less stable structure I CO2-rich hydrate was observed. PXRD data show that the reverse process requires longer initiation times, and structural changes seem to be less complete. Generally, the exchange process can be described as a decomposition and reformation process, in terms of a rearrangement of molecules, and is primarily induced by the chemical potential gradient between hydrate phase and the provided gas phase. The results show furthermore the dependency of the conversion rate on the surface area of the hydrate phase, the thermodynamic stability of the original and resulting hydrate phase, as well as the mobility of guest molecules and formation kinetics of the resulting hydrate phase.

Description: In the colloidal synthesis of iron sulfides, a series of dialkyl disulfides, alkyl thiols, and dialkyl disulfides (allyl, benzyl, tert-butyl, and phenyl) were employed as sulfur sources. Their reactivity was found to tune the phase between pyrite (FeS2), greigite (Fe3S4), and pyrrhotite (Fe7S8). DFT was used to show that sulfur-rich phases were favored when the C–S bond strength was low in the organosulfurs, yet temperature dependent studies and other observations indicated the reasons for phase selectivity were more nuanced; the different precursors decomposed through different reaction mechanisms, some involving the oleylamine solvent. The formation of pyrite from diallyl disulfide was carefully studied as it was the only precursor to yield FeS2. Raman spectroscopy indicated that FeS2 forms directly without an FeS intermediate, unlike most synthetic procedures to pyrite. Diallyl disulfide releases persulfide (S–S)2– due to the lower C–S bond strength relative to the S–S bond strength, as well as facile decomposition in the presence of amines through SN2′ mechanisms at elevated temperatures.

Description: Test specimens of methane hydrate were grown under static conditions by combining cold, pressurized CH4 gas with H2O ice grains, then warming the system to promote the reaction CH4 (g) + 6H2O (s???l) ??? CH4??6H2O. Hydrate formation evidently occurs at the nascent ice/liquid water interface, and complete reaction was achieved by warming the system above 271.5 K and up to 289 K, at 25-30 MPa, for approximately 8 hours. The resulting material is pure methane hydrate with controlled grain size and random texture. Fabrication conditions placed the H2O ice well above its melting temperature before reaction completed, yet samples and run records showed no evidence for bulk melting of the ice grains. Control experiments using Ne, a non-hydrate-forming gas, verified that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting is easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably at temperatures well above its melting point. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T= 140-200 K, Pc= 50-100 MPa, and ????= 10-4-10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to a higher degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; x-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

Description: We describe a new and efficient technique to grow aggregates of pure methane hydrate in quantities suitable for physical and material properties testing. Test specimens were grown under static conditions by combining cold, pressurized CH4 gas with granulated H2O ice, and then warming the reactants to promote the reaction CH4(g) + 6H2O(s→l) → CH4·6H2O (methane hydrate). Hydrate formation evidently occurs at the nascent ice/liquid water interface on ice grain surfaces, and complete reaction was achieved by warming the system above the ice melting point and up to 290 K, at 25−30 MPa, for approximately 8 h. The resulting material is pure, cohesive, polycrystalline methane hydrate with controlled grain size and random orientation. Synthesis conditions placed the H2O ice well above its melting temperature while reaction progressed, yet samples and run records showed no evidence for bulk melting of the unreacted portions of ice grains. Control experiments using Ne, a non-hydrate-forming gas, showed that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting are easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably to temperatures well above its ordinary melting point while reacting to form hydrate. Direct observations of the hydrate growth process in a small, high-pressure optical cell verified these conclusions and revealed additional details of the hydrate growth process. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T = 140−200 K, Pc = 50−100 MPa, and ε = 10-4−10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to an unusually high degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; X-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

Description: Numerical tools are essential for the prediction and evaluation of conventional hydrocarbon reservoir performance. Gas hydrates represent a vast natural resource with a significant energy potential. The numerical codes/tools describing processes involved during the dissociation (induced by several methods) for gas production from hydrates are powerful, but they need validation by comparison to empirical data to instill con fidence in their predictions. In this study, we successfully reproduce experimental data of hydrate dissociation using the TOUGH+HYDRATE (T+H) code. Methane(CH4)hydrate growth and dissociation in partially water- and gas-saturated Bentheim sandstone were spatially resolved using Magnetic Resonance Imaging (MRI), which allows the in situ monitoring of saturation and phase transitions. All the CH4 that had been initially converted to gas hydrate was recovered during depressurization. The physical system was reproduced numerically, usingboth a simplified 2D model and a 3D grid involving complex Voronoi elements. We modeled dissociation using both the equilibrium and the kinetic reaction options in T+H, and we used a range of kinetic parameters for sensitivity analysis and curve fitting. We successfully reproduced the experimental results, which confirmed the empirical data that demonstrated that heattransport was the limiting factor during dissociation. Dissociation was more sensitive to kinetic parameters than anticipated, which indicates that kinetic limitations may be important in short-term core studies and a necessity in such simulations. This is the first time T+H has been used to predict empirical nonmonotonic dissociation behavior, where hydrate dissociation and reformation occurred as parallel events.