Detection of intermolecular homonuclear dipolar coupling in organic rich shale by transverse relaxation exchange.

The mechanism behind surface relaxivity within organic porosity in shales has been an unanswered question. Here, we present results that confirm the existence of intermolecular homonuclear dipolar coupling between solid and liquid phases in sedimentary organic matter. Transverse magnetization exchange measurements were performed on an organic-rich shale saturated with liquid hydrocarbon. Liquid and solid constituents were identified through both sample resaturation and through their T1/T2 ratios. Extensive cross peaks are observed in the T2-T2 exchange spectra between the solid and liquid constituents, indicating an exchange of magnetization between the two phases. This result cannot arise from physical molecular diffusion, and the dissolution energies are too high for chemical exchange, such that the magnetization exchange must arise from intermolecular homonuclear dipolar coupling. These results both confirm a possible source of surface relaxivity in organic matter and emphasize caution in the use of standard porous media interpretations of relaxation results in shales because of coupling between different magnetization environments.

Evaluation of sandstone surface relaxivity using laser-induced breakdown spectroscopy.

Nuclear magnetic resonance (NMR) relaxometry is a common technique used to assess the pore size of fluid-filled porous materials in a wide variety of fields. However, the NMR signal itself only provides a relative distribution of pore size. To calculate an absolute pore size distribution from the NMR data, the material's surface relaxivity needs to be known. Here, a method is presented using laser-induced breakdown spectroscopy (LIBS) to evaluate surface relaxivity in sandstones. NMR transverse and longitudinal relaxation was measured on a set of sandstone samples and the surface relaxivity was calculated from the pore size distribution determined with MICP measurements. Using multivariate analysis, it was determined that the LIBS data can predict with good accuracy the longitudinal (R2∼0.84) and transverse (R2∼0.79) surface relaxivity. Analysis of the regression coefficients shows significant influence from several elements. Some of these are elements previously established to have an effect on surface relaxivity, such as iron and manganese, while others are not commonly associated with surface relaxivity, such as cobalt and titanium. Furthermore, LIBS provides advantages compared to current methods to calibrate surface relaxivity in terms of speed, portability, and sample size requirements. While this paper focuses on geological samples, the method could potentially be expanded to other types of porous materials.

Simultaneous Gaussian and exponential inversion for improved analysis of shales by NMR relaxometry.

Nuclear magnetic resonance (NMR) relaxometry is commonly used to provide lithology-independent porosity and pore-size estimates for petroleum resource evaluation based on fluid-phase signals. However in shales, substantial hydrogen content is associated with solid and fluid signals and both may be detected. Depending on the motional regime, the signal from the solids may be best described using either exponential or Gaussian decay functions. When the inverse Laplace transform, the standard method for analysis of NMR relaxometry results, is applied to data containing Gaussian decays, this can lead to physically unrealistic responses such as signal or porosity overcall and relaxation times that are too short to be determined using the applied instrument settings. We apply a new simultaneous Gaussian-Exponential (SGE) inversion method to simulated data and measured results obtained on a variety of oil shale samples. The SGE inversion produces more physically realistic results than the inverse Laplace transform and displays more consistent relaxation behavior at high magnetic field strengths. Residuals for the SGE inversion are consistently lower than for the inverse Laplace method and signal overcall at short T2 times is mitigated. Beyond geological samples, the method can also be applied in other fields where the sample relaxation consists of both Gaussian and exponential decays, for example in material, medical and food sciences.

Application of binomial-edited CPMG to shale characterization.

Unconventional shale resources may contain a significant amount of hydrogen in organic solids such as kerogen, but it is not possible to directly detect these solids with many NMR systems. Binomial-edited pulse sequences capitalize on magnetization transfer between solids, semi-solids, and liquids to provide an indirect method of detecting solid organic materials in shales. When the organic solids can be directly measured, binomial-editing helps distinguish between different phases. We applied a binomial-edited CPMG pulse sequence to a range of natural and experimentally-altered shale samples. The most substantial signal loss is seen in shales rich in organic solids while fluids associated with inorganic pores seem essentially unaffected. This suggests that binomial-editing is a potential method for determining fluid locations, solid organic content, and kerogen-bitumen discrimination.

Updated methodology for nuclear magnetic resonance characterization of shales.

Unconventional petroleum resources, particularly in shales, are expected to play an increasingly important role in the world's energy portfolio in the coming years. Nuclear magnetic resonance (NMR), particularly at low-field, provides important information in the evaluation of shale resources. Most of the low-field NMR analyses performed on shale samples rely heavily on standard T1 and T2 measurements. We present a new approach using solid echoes in the measurement of T1 and T1-T2 correlations that addresses some of the challenges encountered when making NMR measurements on shale samples compared to conventional reservoir rocks. Combining these techniques with standard T1 and T2 measurements provides a more complete assessment of the hydrogen-bearing constituents (e.g., bitumen, kerogen, clay-bound water) in shale samples. These methods are applied to immature and pyrolyzed oil shale samples to examine the solid and highly viscous organic phases present during the petroleum generation process. The solid echo measurements produce additional signal in the oil shale samples compared to the standard methodologies, indicating the presence of components undergoing homonuclear dipolar coupling. The results presented here include the first low-field NMR measurements performed on kerogen as well as detailed NMR analysis of highly viscous thermally generated bitumen present in pyrolyzed oil shale.

Imaging of multiphase fluid saturation within a porous material via sodium NMR.

We present in this paper a method to monitor multiphase fluid core saturation through measurement of the sodium NMR signal. In a rock core saturated with water and oil, sodium will be present only in the water phase, and therefore can be used to separate the two fluids. Two dimensional sodium images were taken to monitor the movement of brine into oil saturated rock cores. The measured fluid exchange agrees well with expected behavior from traditional core analysis methods. Indications of damage to the rock structure can be seen from the patterns of fluid imbibition.

Correlations between diffusion, internal magnetic field gradients, and transverse relaxation in porous systems containing oil and water.

The main focus in this study is to investigate the correlations between internal magnetic field gradients (G0) and transverse relaxation times in liquid-saturated packings of glass beads of different wettabilities. We show how these correlations can be expressed as two-dimensional (2D) diagrams of distribution functions between internal magnetic field gradients and T2 values. In the case where it is difficult to distinguish the signals from oil and water, we separate them based on their difference in diffusivity. In addition to using such diffusion weighting in the G0-T2 diagrams, we also show results from experiments where the direct correlation between diffusion and T2 (D-T2) is determined. The overall results show that the wettability of the glass beads has a strong influence on the appearance of these diagrams, in particular on the location of the fast diffusing water molecules. However, due to their lower diffusivity, the transverse magnetization of the oil molecules is not so greatly influenced by either the presence of the glass beads or their wettability properties. Thus, the wettability properties of a liquid-filled porous material can be determined from the location of the water signal in such 2D diagrams. In particular, we show that this is the case not only for D-T2 diagrams, but also for G0-T2 diagrams.