Determination of Methane Diffusion Coefficients in Live Oils for Tight Reservoirs at High Pressures

2021 ◽  
Author(s):  
Yibo Yang ◽  
Teresa Regueira ◽  
Hilario Martin Rodriguez ◽  
Alexander Shapiro ◽  
Erling Halfdan Stenby ◽  
...  
Keyword(s):  
High Pressure ◽  
Diffusion Coefficients ◽  
High Pressures ◽  
Diffusion Method ◽  
Pressure Diffusion ◽  
Reservoir Conditions ◽  
Tight Reservoirs ◽  
Methane Diffusion ◽  
Live Oil

Abstract Molecular diffusion plays a critical role in gas injection in tight reservoirs such as liquid-rich shale. Despite recent efforts on measuring diffusion coefficients at high pressures, there is a general lack of the diffusion coefficients in live oil systems at reservoir conditions relevant to the development of these tight reservoirs. The reported diffusion coefficients often differ in orders of magnitude, and there is no consensus on the reliability of the common correlations for liquid phase diffusion coefficients, such as the extended Sigmund correlation. We employed the constant volume diffusion method to measure the high-pressure diffusion coefficients in a newly designed high-pressure tube. The experimental method was first validated using methane + hexadecane and methane + decane, and then used to measure the methane diffusion coefficients in two live oils at reservoir conditions. The obtained data were processed by compositional simulation to determine the diffusion coefficients. The diffusion coefficients measured for methane + hexadecane and methane + decane are in agreement with the existing literature data. For methane + live oil systems, however, the diffusion coefficients estimated by the extended Sigmund correlation are much lower than the measured results. An over ten times adjustment is needed to best fit the pressure decay curves. A further check reveals that for live oil systems, the reduced densities are often in the extrapolated region of the original Sigmund model. The curve in this region of the extended Sigmund correlation has a weak experimental basis, which may be the reason for its large deviation. The estimates from other correlations like Wilke-Chang and Hayduk-Minhas also give very different results. We compared the diffusion coefficients in high-pressure oils reported in the literature, showing a large variation in the reported values. All these indicate the necessity for further study on accurate determination of high-pressure diffusion coefficients in live oils of relevance to shale and other tight reservoirs.

On the Negative Excess Isotherms for Methane Adsorption at High Pressure: Modeling and Experiment

SPE Journal ◽  
2019 ◽  
Vol 24 (06) ◽  
pp. 2504-2525 ◽  
Author(s):  
Jing Li ◽  
Keliu Wu ◽  
Zhangxin Chen ◽  
Kun Wang ◽  
Jia Luo ◽  
...  
Keyword(s):  
High Pressure ◽  
Mass Balance ◽  
High Pressures ◽  
Pore Wall ◽  
Void Volume ◽  
Excess Adsorption ◽  
Experimental Conditions ◽  
Accessible Volume ◽  
Adsorbed Phase

Summary An excess adsorption amount obtained in experiments is always determined by mass balance with a void volume measured by helium (He) –expansion tests. However, He, with a small kinetic diameter, can penetrate into narrow pores in porous media that are inaccessible to adsorbate gases [e.g., methane (CH4)]. Thus, the actual accessible volume for a specific adsorbate is always overestimated by an He–based void volume; such overestimation directly leads to errors in the determination of excess isotherms in the laboratory, such as “negative isotherms” for gas adsorption at high pressures, which further affects an accurate description of total gas in place (GIP) for shale–gas reservoirs. In this work, the mass balance for determining the adsorbed amount is rewritten, and two particular concepts, an “apparent excess adsorption” and an “actual excess adsorption,” are considered. Apparent adsorption is directly determined by an He–based volume, corresponding to the traditional treatment in experimental conditions, whereas actual adsorption is determined by an adsorbate–accessible volume, where pore–wall potential is always nonpositive (i.e., an attractive molecule/pore–wall interaction). Results show the following: The apparent excess isotherm determined by the He–based volume gradually becomes negative at high pressures, but the actual one determined by the adsorbate–accessible volume always remains positive.The negative adsorption phenomenon in the apparent excess isotherm is a result of the overestimation in the adsorbate–accessible volume, and a larger overestimation leads to an earlier appearance of this negative adsorption.The positive amount in the actual excess isotherm indicates that the adsorbed phase is always denser than the bulk gas because of the molecule/pore–wall attraction aiding the compression of the adsorbed molecules. Practically, an overestimation in pore volume (PV) is only 3.74% for our studied sample, but it leads to an underestimation reaching up to 22.1% in the actual excess amount at geologic conditions (i.e., approximately 47 MPa and approximately 384 K). Such an overestimation in PV also underestimates the proportions of the adsorbed–gas amount to the free–gas amount and to the total GIP. Therefore, our present work underlines the importance of a void volume in the determination of adsorption isotherms; moreover, we establish a path for a more–accurate evaluation of gas storage in geologic shale reservoirs with high pressure.

scholarly journals The Takahashi–Bassett Era of Mineral Physics at Rochester in the 1960s

Minerals ◽  
2020 ◽  
Vol 10 (4) ◽  
pp. 344
Author(s):  
William A. Bassett
Keyword(s):  
High Pressure ◽  
High Pressures ◽  
Faculty Position ◽  
Mineral Physics ◽  
High Pressure High Temperature ◽  
High Pressures And Temperatures ◽  
The 1960S ◽  
Talented Students ◽  
The University

The late Taro Takahashi earned a particularly well-deserved reputation for his research at Lamont Geological Observatory on carbon dioxide and its transfer between the atmosphere and the oceans. However, his accomplishments in Mineral Physics, the field embracing the high-pressure–high-temperature properties of materials, has received less attention in spite of his major contributions to this emerging field focused on the interiors of Earth and other planets. In 1963, I was thrilled when he was offered a faculty position in the Geology Department at the University of Rochester, where I had recently joined the faculty. Taro and I worked together for the next 10 years with our talented students exploring the blossoming field just becoming known as Mineral Physics, the name introduced by Orson Anderson and Ed Schreiber, who were also engaged in measuring physical properties at high pressures and temperatures. While their specialty was ultrasonic velocities in minerals subjected to high pressures and temperatures, ours was the determination of crystal structures, compressibilities, and densities of such minerals as iron, its alloys, and silicate minerals, especially those synthesized at high-pressure, such as silicates with the spinel structure. These were materials expected to be found in the Earth’s interior and could therefore provide background for the interpretation of geophysical observations.

The theory of ionisation measurements in gases at high pressures

1934 ◽  
Vol 30 (1) ◽  
pp. 80-101 ◽  
Author(s):  
D. E. Lea
Keyword(s):  
High Pressure ◽  
Experimental Determination ◽  
Experimental Technique ◽  
Alpha Particle ◽  
Reasonable Agreement ◽  
High Pressures ◽  
Industrial Research ◽  
Heavy Nuclei ◽  
Nuclear Tracks

The columnar theory developed by Jaffé to account for the recombination of ions in alpha particle tracks is extended to beta rays by taking account of the clusters of secondary ionisation. Reasonable agreement is obtained with experiment. Recombination in proton tracks produced in hydrogen by neutrons is shown to be in agreement with the columnar theory, but in the case of nitrogen nuclear tracks in nitrogen the recombination is only a hundredth of that predicted by the theory. An explanation of this effect is advanced, and it is suggested that recombination is likely to be abnormally small for all heavy nuclei of velocities not exceeding 5 × 108 cm. per sec.An experimental determination of the coefficient of recombination of ions in nitrogen and hydrogen at pressures of 20, 40 and 90 atmospheres is reported.My thanks are due to Dr Chadwick for interest in this work, and to Dr Gray and Dr Tarrant for advice on the experimental technique of high pressure ionisation measurements. I am indebted also to the Department of Scientific and Industrial Research for a maintenance grant.

Zu Stofftransport und Hydrodynamik der Pulsationsdiffusion

1974 ◽  
Vol 29 (7) ◽  
pp. 1045-1049
Author(s):  
H. Beßerdich ◽  
E. Kahrig ◽  
Fr. Lange
Keyword(s):  
Diffusion Coefficients ◽  
Ternary Mixtures ◽  
Diffusion Method ◽  
Periodic Flow ◽  
Matter Transport ◽  
Binary And Ternary Mixtures ◽  
Transfer Parameters ◽  
Diffusion Separation ◽  
Separation Problems

The pulsation diffusion method is used successfully for the determination of diffusion coefficients in different systems (selfdiffusion, binary and ternary mixtures) and in connection with diffusion separation in liquids. The main advantage is the enhancement of matter transport by periodic flow e. g. in a capillary. Adapting a computation by P. L. Kapiza it is reported on a general treatment for the special conditions in a pulsation diffusion apparatus. Transport behavior depends strongly on hydrodynamic and mass transfer parameters. The results are important for the application of the pulsation method for measuring diffusion coefficients and for separation problems.

Structural characterization of a new high-pressure phase of GaAsO4

2006 ◽  
Vol 62 (6) ◽  
pp. 1019-1024 ◽  
Author(s):  
David Santamaría-Pérez ◽  
Julien Haines ◽  
Ulises Amador ◽  
Emilio Morán ◽  
Angel Vegas
Keyword(s):  
Crystal Structure ◽  
High Pressure ◽  
High Pressures ◽  
Ambient Conditions ◽  
Hexagonal Cell ◽  
Octahedral Sites ◽  
New Phase ◽  
Pressure Phase

As in SiO2 which, at high pressures, undergoes the α-quartz → stishovite transition, GaAsO4 transforms into a dirutile structure at 9 GPa and 1173 K. In 2002, a new GaAsO4 polymorph was found by quenching the compound from 6 GPa and 1273 K to ambient conditions. The powder diagram was indexed on the basis of a hexagonal cell (a = 8.2033, c = 4.3941 Å, V = 256.08 Å3), but the structure did not correspond to any known structure of other AXO4 compounds. We report here the ab initio crystal structure determination of this hexagonal polymorph from powder data. The new phase is isostructural to β-MnSb2O6 and it can be described as a lacunary derivative of NiAs with half the octahedral sites being vacant, but it also contains fragments of the rutile-like structure.

Design and Analysis of a High Pressure Apparatus

1980 ◽  
Vol 102 (3) ◽  
pp. 633-640
Author(s):  
K. C. Rolle ◽  
J. N. Crisp ◽  
A. N. Palazotto
Keyword(s):  
Finite Element ◽  
High Pressure ◽  
Phase Diagrams ◽  
High Pressures ◽  
Equilibrium Phase ◽  
Original Design ◽  
Piston Displacement ◽  
Crude Analysis ◽  
High Pressure Apparatus

In the determination of equilibrium phase diagrams, i.e., pressure volume-temperature relations for lubricants at pressures up to 2800 MPa and temperatures of 378K, one must carry out a highly sophisticated design of a high pressure apparatus. In 1935 Bridgman designed a piston-displacement device and measured the compressibility of numerous materials at high pressures. However, in order to obtain accurate equilibrium phase diagrams for lubricants, Bridgman’s relatively crude analysis must be considerably refined. The authors have extended this original design using finite element techniques to accurately correct pertinent measurements which are in turn incorporated into the expressions used in determining the pressure-volume temperature relations of lubricants.

Some Methodological Modifications of Determination of Diffusion Coefficients in Compacted Bentonite

2006 ◽  
Vol 932 ◽  
Author(s):  
Dušan Vopálka ◽  
Helena Filipská ◽  
Antonín Vokál
Keyword(s):  
Diffusion Coefficients ◽  
Effective Porosity ◽  
Diffusion Method ◽  
Dry Density ◽  
Diffusion Cell ◽  
Compacted Bentonite ◽  
Method Of Evaluation ◽  
Exclusion Effect ◽  
Positively Charged

ABSTRACTThe results of 3H, 36Cl and 137Cs diffusion experiments through compacted bentonite using a new design of diffusion cell and a new methodology of diffusion coefficients evaluation are presented. The diffusion cell was made from the stainless steel and enables to connect it directly to the input and/or output reservoirs without any tubing. The evaluation of diffusion coefficients utilizes a compartmental model developed in the environment of the GoldSim transport code. It enables to determine diffusion coefficients for various types of boundary conditions, including also input and output filters. The influence of the diffusion through filters on the determined values of both effective (De) and apparent (Da) diffusion coefficients was numerically demonstrated for the through diffusion method. This effect is most important for Da, the value of which would be underestimated using standard ways of evaluation for neutral and positively charged species, mainly in the case of high effective porosity.The comparison of standard and the newly developed method of evaluation of diffusion coefficients showed a significant influence of diffusion in filters for HTO. Contrary to the standard method of evaluation, the evaluation taking into account filters showed here no difference between total and effective porosity. The effect of filter resistance was negligible for Cl-, especially at high dry density of compacted bentonite, due to the anion exclusion effect. The numerical model developed enabled to determine Da values of Cs+ from the concentration change in the inlet reservoir.

A Corresponding States Correlation for Calculating Gas-Condensate Phase Equilibria

1968 ◽  
Vol 8 (03) ◽  
pp. 281-292 ◽  
Author(s):  
Alan S. Emanuel
Keyword(s):  
Phase Equilibria ◽  
Phase Behavior ◽  
High Pressures ◽  
Experimental Studies ◽  
Corresponding States ◽  
Gas Condensate ◽  
Reference Substance ◽  
K Value ◽  
Reservoir Conditions

Abstract A correlation has been developed for calculating the phase behavior of gas-condensate systems at reservoir conditions. The correlation is based on the principle of corresponding states and has been coded for an IBM 7094. Experimental K-values were determined for several gas-condensate systems at reservoir conditions to evaluate various semiempirical parameters of the correlation. The approximate range of application of the correlation is 150 to 300F and 1,500 to 6,000 psi. Introduction The rapid development of digital computers during the past several years has made feasible the calculation of hydrocarbon phase behavior by methods based on rigorous thermodynamic principles. Good correlations have been developed for low to moderate pressures, but these techniques have not yet been extended successfully to reservoir fluids at high pressures. Consequently, the determination of phase behavior of oil and gas systems at reservoir conditions is still based almost entirely on generalized data correlations or on experimental studies of the fluid in question. While these methods have been used successfully many times, they do have inherent limitations that restrict their applicability. Generalized correlations, such as the NGSMA K-charts, are limited to the range of pressure, temperature and components for which pressure, temperature and components for which the data were determined. The accuracy of these correlations is often questionable because the effect of total system composition is not well defined. Experimental studies offer a reliable method for determining phase behavior, but usually the studies are costly and time consuming. Recently, Leland and coworkers presented a new approach to calculating phase behavior from the principles of corresponding states. Corresponding states methods determine the thermodynamics properties of a given system by comparison with a reference substance whose properties are known. The accuracy of data properties are known. The accuracy of data approach depends on close chemical and structural similarity between the reference substance and the system in question and between components within the system itself. For high accuracy, it is usually necessary to correct for chemical and structural dissimilarities. In principle, however, the corresponding states method should be no less accurate at high pressures than at low pressures, provided reference substance properties are known. provided reference substance properties are known. This paper describes an empirical modification of the basic correlation proposed by Leland, et al. for the specific purpose of calculating the phase behavior of gas-condensate fluids at reservoir conditions. The modified correlation, which has been Programmed for an IBM 7094, may be used for either approximate or precise determination of fluid behavior depending on the amount of analytical and, experimental data available for the system. BASIC THEORY The basic theory of the corresponding states phase equilibria correlation was first published by phase equilibria correlation was first published by Leland, Chappelear and Gamson. Subsequently, Leland, Chappelear and Leach published methods for improving me accuracy of the original theory. The aim of the correlation is to calculate the K-value of each component of a given system as a function of pressure, temperature, and over-all composition, where ..........................................(1) Once the K-values are known, the phase behavior may be determined directly by an appropriate flash calculation. The basic equation for calculating component K-values was taken from the work of Joffe. For any component i of a mixture, the K-value is given by ..........................................(2) SPEJ P. 281

Hochdruckumwandlungen von Cer(III)Orthovanadat(V), CeVO4 / High-Pressure Transformations of Cerium(III) Orthovanadate(V), CeVO4

1990 ◽  
Vol 45 (5) ◽  
pp. 598-602 ◽  
Author(s):  
Klaus-Jürgen Range ◽  
Helmut Meister ◽  
Ulrich Klement
Keyword(s):  
High Pressure ◽  
Triple Point ◽  
High Pressures ◽  
Its Region ◽  
Normal Pressure ◽  
Crystal Data ◽  
High Pressures And Temperatures ◽  
Zircon Type ◽  
High Pressure Apparatus

The polymorphism of CeVO4 was investigated at high pressures and temperatures in a Belttype high-pressure apparatus. In addition to the normal-pressure modification CeVO4— I with zircon-type structure two high-pressure modifications have been found, viz. monazite-type CeVO4—II and scheelite-type CeVO4—III. CeVO4—II is stable between 1 bar and 30 kbar at 1300 °C. Its region of existence decreases rapidly at lower temperatures. From the observed p,T-relations for the I-II and I-III transformations a triple point CeVO4—I,II,III at about 27 kbar, 500 °C can be estimated. For kinetic reasons, however, the experimental determination of phase relations becomes difficult at temperatures below 600 °C.The crystal structures of CeVO4— I and —II have been refined from single-crystal data. Crystallographic data for the three modifications are given and discussed (CeVO4—I: I 41/amd, a = 7.383(1)Å, c = 6.485(1)Å, Z = 4; CeVO4—II: P21/n, a = 7.003(1)Å, b = 7.227(1)Å, c = 6.685(1)Å, β = 105.13(1)°, Z = 4; CeVO4—III: I 41/α, a = 5.1645(2)Å, c = 11.8482(7)Å, Z = 4).

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