scholarly journals Measurement of pore sized microporous-mesoporous materials by time-domain nuclear magnetic resonance

BioResources ◽  
2020 ◽  
Vol 15 (1) ◽  
pp. 1407-1418
Author(s):  
Zhi-hong Zhao ◽  
Ming-hui Zhang ◽  
Wen-Jing Liu ◽  
Quan-teng Li
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Relaxation Rate ◽  
Porous Materials ◽  
Pore Size ◽  
Mesoporous Materials ◽  
Time Domain ◽  
Surface Relaxation ◽  
Pore Surface ◽  
Anodized Aluminum

Time-domain nuclear magnetic resonance (TD NMR) technology has been used for pore detection in porous materials for a long time, but there are few pore detection methods for microporous-mesoporous materials. The surface of different materials is obtained by pore detection of known pore materials. Relaxation rate, which obtains aperture information, has an important practical significance for the application of time-domain NMR technology in the characterization of porous materials. In this study, the T2 peaks of pores of known pore size materials, namely zeolite molecular sieves (0.3 nm and 1 nm) and anodized aluminum porous membranes (30 nm and 90 nm), were used to calculate the pore surface relaxation of zeolite molecular sieve with 0.3 nm pore size and 1 nm pore size. The ratio of the rate of the surface is 3.379; the ratio of the pore surface relaxation ratio of the 30 nm and 90 nm apertures of the anodized aluminum porous film is 3.031. This result is very close to the pore size ratio, indicating that the surface relaxation rate of the same material is directly related to the pore size, while the T2 peak can qualitatively measure the pore size.

scholarly journals Probe material choice for nuclear magnetic resonance cryoporometry (NMRC) measurements of the nano-scale pore size distribution of unconventional reservoirs

2018 ◽  
Vol 37 (1) ◽  
pp. 412-428
Author(s):  
Feng Zhu ◽  
Wenxuan Hu ◽  
Jian Cao ◽  
Biao Liu ◽  
Yifeng Liu ◽  
...  
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Pore Size Distribution ◽  
Porous Materials ◽  
Pore Size ◽  
Size Distribution ◽  
Geological Samples ◽  
Nano Scale ◽  
Chloride Hexahydrate ◽  
Nuclear Magnetic

Nuclear magnetic resonance cryoporometry is a newly developed technique that can characterize the pore size distribution of nano-scale porous materials. To date, this technique has scarcely been used for the testing of unconventional oil and gas reservoirs; thus, their micro- and nano-scale pore structures must still be investigated. The selection of the probe material for this technique has a key impact on the quality of the measurement results during the testing of geological samples. In this paper, we present details on the nuclear magnetic resonance cryoporometric procedure. Several types of probe materials were compared during the nuclear testing of standard nano-scale porous materials and unconventional reservoir geological samples from Sichuan Basin, Southwest China. Gas sorption experiments were also carried out on the same samples simultaneously. The KGT values of the probe materials octamethylcyclotetrasiloxane and calcium chloride hexahydrate were calibrated using standard nano-scale porous materials to reveal respective values of 149.3 Knm and 184 Knm. Water did not successfully wet the pore surfaces of the standard controlled pore glass samples; moreover, water damaged the pore structures of the geological samples, which was confirmed during two freeze-melting tests. The complex phase transition during the melting of cyclohexane introduced a nuclear magnetic resonance signal in addition to that from liquid in the pores, which led to an imprecise characterization of the pore size distribution. Octamethylcyclotetrasiloxane and calcium chloride hexahydrate have been rarely employed as nuclear magnetic resonance cryoporometric probe materials for the testing of an unconventional reservoir. Both of these materials were able to characterize pore sizes up to 1 μm, and they were more applicable than either water or cyclohexane.

Pore-Size Distributions for Organic-Shale-Reservoir Rocks From Nuclear-Magnetic-Resonance Spectra Combined With Adsorption Measurements

SPE Journal ◽  
2015 ◽  
Vol 20 (04) ◽  
pp. 824-830 ◽  
Author(s):  
Richard F. Sigal
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Pore Size ◽  
Surface Relaxation ◽  
Size Distributions ◽  
Pore Sizes ◽  
Pore Size Distributions ◽  
Shale Reservoirs ◽  
Organic Shale ◽  
Nuclear Magnetic

Summary The behavior of fluids in nanometer-scale pores can have a strong functional dependence on the pore size. In mature organic-shale reservoirs, the nuclear-magnetic-resonance (NMR) signal from methane decays by surface relaxation. The methane NMR spectrum provides an uncalibrated pore-size distribution for the pores that store methane. The distribution can be calibrated by calculating a pore-wall-surface area from a methane-Langmuir-adsorption isotherm. When this method was applied to samples from a reservoir in the dry-gas window, the pores containing methane had pore sizes that ranged from 1 to approximately 100 nm. Approximately 20–40% of the pore volume was in pores smaller than 10 nm, where deviation from bulk-fluid behavior can be significant. The samples came from two wells. The surface relaxivity for the sample from Well 2 was somewhat different from the relaxivity for the two samples from Well 1. Samples that adsorbed more methane had smaller pore sizes. This methodology to obtain pore-size distributions should be extendable to more-general organic-shale reservoirs.

Paramagnetic nanoparticles as nuclear magnetic resonance contrast agents in sandstone: Importance of nanofluid-rock interactions

2016 ◽  
Vol 4 (2) ◽  
pp. SF55-SF65 ◽  
Author(s):  
Chunxiao Zhu ◽  
Hugh Daigle ◽  
Steven L. Bryant
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Relaxation Time ◽  
Magnetic Resonance ◽  
Pore Size ◽  
Pore Surface ◽  
Mineral Surface ◽  
Surface Relaxivity ◽  
Charged Nanoparticles ◽  
Positively Charged ◽  
Zirconia Nanoparticles

Nuclear magnetic resonance has been applied in well logging to investigate pore size distribution with high resolution and accuracy based on the relaxation time distribution. However, due to the heterogeneity of natural rock, pore surface relaxivity, which links relaxation time and pore size, varies within the pore system. To analyze and alter pore surface relaxivity, we saturated Boise sandstone cores with positively charged zirconia nanoparticle dispersions in which nanoparticles can be adsorbed onto the sandstone pore wall, while negatively charged zirconia nanoparticles dispersions were used as a control group to provide the baseline of nanoparticle retention due to nonelectrostatic attraction. We have performed core flushing with deionized water, pure acid, and alkali with different pH values; compared properties of zirconia nanoparticles before and after exposure to Boise sandstone; analyzed the portion of zirconia nanoparticles retained in the rock; altered pore surface relaxivity; and linked the adsorbed nanoparticle concentration on the pore surface to the modified surface relaxivity. Our work has indicated that after two pore volumes of core flooding, there was approximately 1% of negatively charged nanoparticles trapped in the Boise sandstone core, whereas approximately 8%–11% of positively charged nanoparticles was retained in the Boise sandstone cores. Our results indicated that besides van der Waals attraction, electrostatic attraction was the driving force for retention of nanoparticles with a positive surface charge in sandstone cores. The attachment of nanoparticles onto sandstone surfaces changed the mineral surface relaxivity. Exposure to acidic or strong alkaline conditions increased the Boise sandstone surface relaxivity. After contact with Boise sandstone, the nanoparticles themselves exhibited increased relaxivity due to interactions between nanoparticles dispersion and mineral surface under different pH conditions.

Nuclear magnetic resonance surface relaxation mechanisms of kerogen

Geophysics ◽  
2017 ◽  
Vol 82 (6) ◽  
pp. JM15-JM22 ◽  
Author(s):  
Boyang Zhang ◽  
Hugh Daigle
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Hydrogen Bonding ◽  
Magnetic Resonance ◽  
Relaxation Rate ◽  
Dipolar Coupling ◽  
Surface Relaxation ◽  
Proton Density ◽  
Transverse Relaxation Rate ◽  
Pore Fluids ◽  
Transverse Relaxation

Nuclear magnetic resonance (NMR) relaxometry is an excellent tool for probing the interactions between solid pore surface and pore fluids in porous media. Surface relaxation is a key component of NMR relaxation. It is well-known that in conventional rocks, paramagnetic centers contribute most to the surface relaxation phenomenon. However, the interactions between organic pore surfaces and pore fluids, and the mechanism of surface relaxation in organic shale pores, are not well-understood. We tackle the issue using deuterated compounds to adjust the proton density in the liquid phase and monitoring the transverse relaxation rate changes of kerogen-fluid mixtures. With the Barnett and Eagle Ford kerogen isolates, we found that for alkanes, it is intramolecular dipolar coupling that dominates among the magnetic interactions. As a result, the transverse relaxation rate of alkane proton spins is more likely to be dependent on the concentration of active adsorption sites on the kerogen surface, rather than the kerogen proton density. For water inside organic pores, surface relaxation most likely originates from hydrogen bonding and intermolecular dipolar coupling. We also examined the temperature effect on kerogen surface relaxation and found temperature-dependent behavior that is consistent with surface relaxation by hydrogen bonding and homonuclear dipolar coupling interactions.

Textural and pore size analysis of carbonates from integrated core and nuclear magnetic resonance logging: An Arbuckle study

2015 ◽  
Vol 3 (1) ◽  
pp. SA77-SA89 ◽  
Author(s):  
John Doveton ◽  
Lynn Watney
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Relaxation Time ◽  
Magnetic Resonance ◽  
Pore Size ◽  
Relaxation Times ◽  
T2 Relaxation Time ◽  
T2 Relaxation ◽  
Nmr Logging ◽  
The Core ◽  
Nuclear Magnetic

The T2 relaxation times recorded by nuclear magnetic resonance (NMR) logging are measures of the ratio of the internal surface area to volume of the formation pore system. Although standard porosity logs are restricted to estimating the volume, the NMR log partitions the pore space as a spectrum of pore sizes. These logs have great potential to elucidate carbonate sequences, which can have single, double, or triple porosity systems and whose pores have a wide variety of sizes and shapes. Continuous coring and NMR logging was made of the Cambro-Ordovician Arbuckle saline aquifer in a proposed CO2 injection well in southern Kansas. The large data set gave a rare opportunity to compare the core textural descriptions to NMR T2 relaxation time signatures over an extensive interval. Geochemical logs provided useful elemental information to assess the potential role of paramagnetic components that affect surface relaxivity. Principal component analysis of the T2 relaxation time subdivided the spectrum into five distinctive pore-size classes. When the T2 distribution was allocated between grainstones, packstones, and mudstones, the interparticle porosity component of the spectrum takes a bimodal form that marks a distinction between grain-supported and mud-supported texture. This discrimination was also reflected by the computed gamma-ray log, which recorded contributions from potassium and thorium and therefore assessed clay content reflected by fast relaxation times. A megaporosity class was equated with T2 relaxation times summed from 1024 to 2048 ms bins, and the volumetric curve compared favorably with variation over a range of vug sizes observed in the core. The complementary link between grain textures and pore textures was fruitful in the development of geomodels that integrates geologic core observations with petrophysical log measurements.

Objective-Driven Solid-Surface-Roughness Characterization for Enhanced Nuclear-Magnetic-Resonance Petrophysics

SPE Journal ◽  
2021 ◽  
pp. 1-20
Author(s):  
Shouxiang Mark Ma ◽  
Gabriela Singer ◽  
Songhua Chen ◽  
Mahmoud Eid
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Surface Roughness ◽  
Magnetic Resonance ◽  
Pore Size ◽  
Solid Surface ◽  
Micro Ct ◽  
Roughness Effects ◽  
Formation Evaluation ◽  
Petrophysical Parameters ◽  
Rock Types

Summary Typically, smooth solid surfaces of reservoir rocks are assumed in formation evaluation, such as nuclear-magnetic-resonance (NMR) petrophysics and reservoir-wettability characterization through contact-angle measurements. Measuring the degree of surface roughness (R), or smoothness, and evaluating its effects on formation evaluation are topics of much research. In this paper, we primarily focus on details in characterizing solid-surface roughness and its applications in NMR pore-sizeanalysis. R can be measured by contact techniques and noncontact techniques, such as stylus profilometer, atomic-force microscopy, and different kinds of optical measurements. Each technique has different sensitivities, measurement artifacts, resolutions, and field of view (FOV). Intuitively, although a finer resolution measurement provides the closest account of all surface details, the correspondingly small FOV might compromise the representativeness of the measurement, which is particularly challenging for charactering heterogeneous samples such as carbonates. To balance the FOV and measurement representativeness, and to minimize artifacts, laser scanner confocal microscopy (LSCM) is selected in this study. Results for the more than 27 rock samples tested indicate that rocks of similar rock types have similar R-values. Grainy limestones have relatively higher R-values compared with dolostones, consistent with the dolostone’s crystallization surface features. Muddy limestones have smoother surfaces, resulting in the lowest R-values among the rocks studied. For sandstones, R varies with clay types and content. For rocks containing two distinct minerals, two R-values are observed from the R profiles, which for these rock types justifies the use of two NMR surface relaxivity (ρ2) parameters for determining the pore-size distribution (PSD) from the NMR T2distribution. The novelty here is the integration of LSCM and NMR to obtain an NMR PSD relevant for permeability, capillary pressure, and other petrophysical parameters. Typically, ρ2 is calibrated using the total surface area from Brunauer-Emmett-Teller (BET; Brunauer et al. 1938) gas adsorption, but this underestimates the NMR pore size because of surface-roughness effects. In our novel approach, we use R measured from LSCM to correct ρ2 for surface-roughness effects, and thereby obtain the NMR pore size more relevant for permeability and other petrophysical parameters. We then compare the roughness-corrected NMR PSD against pore size from microcomputed tomography (micro-CT) scanning (which is roughness independent). The good agreement between roughness-corrected NMR and micro-CT pore sizes in the micropore region validates our new technique, and highlights the importance of surface-roughness characterization in NMR petrophysics.

scholarly journals Nuclear Magnetic Resonance Spectroscopy for In Situ Monitoring of Porous Materials Formation under Hydrothermal Conditions

Materials ◽  
2018 ◽  
Vol 11 (8) ◽  
pp. 1416 ◽  
Author(s):  
Mohamed Haouas
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Porous Materials ◽  
Local Environment ◽  
In Situ Monitoring ◽  
Resonance Spectroscopy ◽  
Hydrothermal Conditions ◽  
Technological Advances ◽  
Nuclear Magnetic

The employment of nuclear magnetic resonance (NMR) spectroscopy for studying crystalline porous materials formation is reviewed in the context of the development of in situ methodologies for the observation of the real synthesis medium, with the aim of unraveling the nucleation and growth processes mechanism. Both liquid and solid state NMR techniques are considered to probe the local environment at molecular level of the precursor species either soluble in the liquid phase or present in the reactive gel. Because the mass transport between the liquid and solid components of the heterogeneous system plays a key role in the synthesis course, the two methods provide unique insights and are complementary. Recent technological advances for hydrothermal conditions NMR are detailed and their applications to zeolite and related materials crystallization are illustrated. Achievements in the field are exemplified with some representative studies of relevance to zeolites, aluminophosphate zeotypes, and metal-organic frameworks.

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