What is the shape of pores in natural rocks?

Quan Chen and Y.-Q. Song Citation: The Journal of Chemical Physics 116, 8247 (2002); doi: 10.1063/1.1477183 View online: http://dx.doi.org/10.1063/1.1477183 View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/116/19?ver=pdfcov Published by the AIP Publishing

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JOURNAL OF CHEMICAL PHYSICS

VOLUME 116, NUMBER 19

15 MAY 2002

COMMUNICATIONS What is the shape of pores in natural rocks?

Quan Chen
Institute of Porous Flow and Fluid Mechanics, China National Petroleum Co. and Chinese Academy of Sciences, P.O Box 44, Langfang, Hebei, 065007, China

Y.-Q. Song
Schlumberger-Doll Research, Ridgeeld, Connecticut 06877

Received 10 January 2002; accepted 19 March 2002 The geometry of the internal space of porous media determines transport properties at all scales. We demonstrate an experimental scheme to quantify the body-to-throat ratio and the shape of the pores through direct measurements of geometrical quantities. We used a constant-rate mercury injection measurement to obtain the throat size and the pore-body volume, and an NMR method DDIF to obtain the pore size distribution in a Berea sandstone. This approach uniquely identies the pore throats and bodies and enables a quantication of their sizes. Our results show that the pore bodies in Berea sandstone is likely to be described by a very much elongated cavity. 2002 American Institute of Physics. DOI: 10.1063/1.1477183

INTRODUCTION

Internal space of porous media can often be described as a series of cavities connected by smaller channels, or throats, that can be visualized by three-dimensional imaging.1 4 The shape of the cavities, or pore bodies and their relative size to the throat are important characteristics determining multiphase uid ow.5 Bulk measurements of these geometrical parameters are needed for understanding uid ow on the relevant size scale. For example, mercury porosimetry has long been used to characterize pore throat6 8 and was shown9 to correlate with permeability in some rocks. However, full experimental characterization of the pore geometry remains difcult owing to the complexity of the pore space. For example, the conventional mercury porosimetry operates by incrementing the injection pressure and recording the injected mercury volume at each step. Such a pressurecontrolled porosimetry measures only pore throat size and does not detect the size of the pore body behind the throats. Thus, the different pore systems may yield the same capillary pressure curve. Also, pore shape can be probed indirectly using the effect of restricted diffusion.1014 In this paper, we demonstrate a scheme to combine two types of experiments to identify the geometry of pore throats and pore bodies. This allows us to determine different characteristics of the pore space on one sample in order to deduce detailed pore geometry information. We will describe the experiment techniques before presenting the results.
TECHNIQUES

monitors the uctuations of the injection pressure. The injection rate is kept extremely low so that the pressure loss due to ow inside the sample is negligible compared to the capillary pressure. A fraction of the CRMI data of injection pressure as a function of injection volume is shown in Fig. 1. The observation of a sudden pressure drop, referred to as rheon, 16 20 is a result of the movement of a single mercury meniscus from a narrow region pore throat into a wider region pore body, accompanied by a simultaneous mercury redistribution within the pore space. The use of the terms throat and body here does not imply a specic pore model. In fact, the pressure uctuations observed during injection indicate unambiguously the presence of connected regions of small and larger dimensions that are called throats and bodies, respectively. Such a denition of body and throat is most relevant to ow in the material. The pore throat radius r can be obtained directly from the entry pressure at the start of the rheon using YoungLaplace equation:21 P e 2 cos / r . 1

One technique we used is constant rate mercury injection CRMI.15 This technique has been applied to many porous materials and we only present here a brief description of its operation. CRMI is different from the conventional mercury injection in that it maintains a constant injection rate and
0021-9606/2002/116(19)/8247/4/$19.00 8247

Here, P e is the mercury entry pressure, is the mercuryvacuum interfacial tension, the contact angle. This equation assumes that the principal radii of curvature of the mercury meniscus are equal. The subsequent rise of the injection pressure subison corresponds to the lling of the pore body until the entry pressure is reached again. Further increase in injection pressure rison is due to the lling of pore throat. The terms of subison and rison were introduced by Yuan and Swanson.15 A subison system may consist of a single pore body or a group of several pore bodies. Secondary and higher-order rheons may divide a subison into compartments. The pore body volume can be determined from the injection rate and the time period to ll the subison or compartments.
2002 American Institute of Physics

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Q. Chen and Y.-Q. Song

FIG. 2. DDIF spectrum circles for the Berea sandstone performed on the hydrogen nuclei in the brine water. The pore diameter distribution shows a predominate peak at about 85 m. The line is an accumulative integral of the DDIF spectrum. FIG. 1. CRMI injection pressure vs volume on the Berea sandstone sample of 1.5 ml volume with a porosity of 20% and permeability 0.2 D. The two lines are raw CRMI data and the corrected data by a calibration run using a stainless steel test sample of the same size. Transducer noise was also ltered. The amount of the correction is quite small and the two data sets overlap. Inset: CRMI pore body volume distribution showing a predominate peak at around 20 nl.

In addition to obtaining the mercury capillary curve, such a CRMI experiment identies the pore body and pore throat. The second technique we used is a recently developed method DDIF22 to determine pore size distribution using nuclear magnetic resonance NMR. This method has been shown22 to create a spatial pattern of nuclear spin magnetization modulation within individual pores and the decay time constant of such modulation due to molecular diffusion is directly related to the pore size. The mechanism to produce such magnetization modulation is the use of the magnetic eld inhomogeneity due to magnetic susceptibility contrast between the uid and solid materials.2325 A DDIF experiment creates and detects the magnetization modulation using three radio-frequency rf pulses in a stimulated echo sequence:26

/2 t e /2 T d /2 t e echo.

The symbol /2 denotes a rf pulse that rotates the spin vector by 90 degrees. t e and T d are time periods separating the rf pulses. The magnetization modulation is created during the rst two pulses and an echo signal is detected at a t e time period after the third pulse. Typically, t e is on the order of tens to hundreds of microseconds. Measurements are made for a series of T d times ranging from 10 s to several seconds. It is during the T d period that the decay of the magnetization modulation occurs. The measured echo signal as a function of T d is often a multi-exponential decay and a numerical Laplace inversion algorithm is used to obtain the size distribution of pores, including bodies and throats. The details of the measurement and the analysis methods are described in Refs. 22,27.
EXPERIMENT

volume 1.5 cc. The two samples came from close proximity of each other and they were expected to have a similar pore structure. The CRMI experiments were carried out on an ASPE7301 porosimetry Coretest Systems, Inc. which consisted of a Quizix SP5000 series pump cylinder with an integrated core holder equipped with a pressure transducer port and a bleed port. The system allowed a very low injection rate with a resolution of 0.1 nl/s. An injection rate of 0.7 nl/s was used in our experiment. The core holder was designed to accommodate a cubic or cylindrical sample of up to 2.54 cm in diameter and 2.54 cm long. A high accuracy 0.05% pressure transducer of 1000 psi full-scale range was interfaced with a 22 bit analog-to-digital converter giving a nal pressure resolution of 0.01 psi. The core holder and pumping system were enclosed in a horizontal forced ow air bath with a temperature stability of about 1 C. Injection data, including volume, pressure, time and temperature were logged to a PC every second. The DDIF experiment was performed on hydrogen nuclei at a 2 T magnetic eld Nalorac Cryogenics Co. using a Bruker Biospec spectrometer. We used t e 50 s, and a series of 35 values of T d spanning from 10 s to 3 s logarithmically. The /2 pulses were 10 s long. Four scans was performed for phase cycling and signal averaging.
RESULTS AND DISCUSSION Pore size distribution

A Berea sandstone sample was used in our experiments. Its porosity is 20% and permeability 0.2 D. The size of the NMR sample is 2.0 cm in diameter and 3.8 cm long, and saturated with brine water. The sample for CRMI is a cube of

We begin by showing the pore size distribution obtained from the DDIF experiment, in Fig. 2. This result provides a measure of the linear dimension of pores, including pore bodies and throats. The spectrum shows a predominate peak at about 85 m and a shoulder extending to a few micron at a reduced amplitude. This spectrum is consistent with those obtained for several other Berea sandstone samples in previous work.28 It has been shown22 that the DDIF method can identify pores of different sizes even when they are closely packed together. On the other hand, this spectrum alone does not provide information about the connectivity of the pores. Henceforth, combining pore throat information from mercury injection experiment and DDIF will allow us to probe the pore connectivity.

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J. Chem. Phys., Vol. 116, No. 19, 15 May 2002

What is the shape of pores in natural rocks

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FIG. 3. Pore throat diameter distribution for the Berea sandstone sample with CRMI method lled squares and conventional Hg porosimetry open squares. The observation of a narrow peak at around 15 m and a small shoulder extending to small throat size is consistent for the two measurement methods.

Pore throat

The conventional mercury injection experiment was performed and the obtained mercury capillary curve is shown in Fig. 3. It shows a single peak at about 15 m with a small shoulder down to a few m. Similar to previous observations in other Berea sandstone samples,28 the length scale of the mercury peak occurs right inside the DDIF pore size distribution Fig. 2. This indicates unambiguously that the pores shown as the peak in the DDIF spectrum are connected through throats that are about 15 m in size. Using CRMI data, we have also computed the total mercury capillary curve displayed in Fig. 3. Results from the two methods are very consistent with each other for both the narrow peak at around 15 m and the shoulder to small throat sizes. This conrmed that in our CRMI measurement, the pressure drop due to ow was negligible and the capillary pressure was well represented by the injection pressure. The one important advantage of CRMI is that it is able to partition the injection volume into throats and pore bodies. The pore body is associated with the sudden drop and the subsequent rise of the injection pressure. Thus, one can obtain a distribution of the pore body volume by counting the number of rheons and the associated injection volume. In addition, the CRMI measurement also determined the pore throat volume and the ratio of pore-body volume to porethroat volume was found to be 1.85. We may compare this throat porosity faction with the DDIF result. DDIF spectrum in Fig. 2 shows that the porosity below 25 m is approximately 33%, a value that is quite close to the porosity fraction of the throats from CRMI. This concludes that the pore body volume dominates the total pore volume of the Berea sandstone sample. Second, the porosity below 25 m is mostly throats and that above 25 m is pore bodies.
Pore body shape

FIG. 4. The transmission optical micrograph of the Berea sandstone section of 30 m thick. The gray regions are large quartz crystals and the dark regions are small crystals and clay. The white regions are pore space identied by the color of the epoxy impregnation prior to sectioning. The eld of view is 1228 by 921 m. Many cavities of the size of 85 m are apparent.

The pore body volume distribution from CRMI is illustrated in the inset of Fig. 1, showing a predominate peak at around 20 nl. This result is consistent with that of Yuan and Swanson15 on Berea sandstone. Since there is a rapid redistribution of mercury at rheon, the injection pressure is not related well to the size of the pore body. Thus, the pore-body volume data alone does not determine the shape of the pores. A usual assumption of a spherical pore will give a pore di-

ameter of 340 m, which is inconsistent with the thinsection micrograph and the DDIF result that the pore body size is about 85 m in this sample. This clearly indicates that the pore body is far from a spherical shape. Given the pore body volume and one of the linear dimension from DDIF, two shapes are possible, a pancake-like oblate or a tube-like oblong, with the short axis being 85 m. Both of them would satisfy the observed DDIF pore size distribution. However, their 2D sections would be substantially different. Imagine that one cuts a long tube at random positions and orientations. The cross-section images would be dominated by ellipses of the size of the tube diameter, corresponding to sections perpendicular to the tubes long axis. In addition, there will be some sections showing elongated ellipses corresponding to the sections parallel to the long axis of the tube. On the other hand, sections of an oblate would be dominated by the elongated ellipses, and there will be no sections that approximate circles with a diameter of the short axis. In Fig. 4, we show a thin-section micrograph of our sample. It is apparent that the majority of the pores are not extensively elongated and they are better described by a small aspect ratio. A few of the pores, on the other hand, are quite extended, up to several hundreds m, such as the one indicated by the circle in Fig. 4. Thus, we conclude that the shape of the pore bodies in Berea sandstone can be described as long tube. Taking the average shape of the pore body to be tube of a diameter of 85 m, the corresponding length would be 0.35 cm. Note that the straight tube is likely to be an oversimplied model, the value of the corresponding length should be considered only qualitative. Since a typical grain in Berea sandstone is about 200 400 m in diameter, the elongated pore body may likely form a tunnel, possibly with branches, wrapped around several grains. It is unlikely that it will form a straight cylinder. This is also consistent with the lack of very long pores in the 2D sections. Furthermore, it is possible that the several pores appearing around a grain in 2D sections, in fact, are connected in three dimension belonging to the same pore body. From 3D x-ray tomograph of

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Q. Chen and Y.-Q. Song Ramakrishnann, D. H. Rothman, and L. M. Schwartz, Geophys. Res. Lett. 23, 705 1996. 4 Y. Sakamoto, M. Kaneda, O. Terasaki, D. Y. Zhao, J. Kim, G. Stucky, H. Shin, and R. Ryoo, Nature London 408, 449 2000. 5 F. A. L. Dullien, Porous Media: Fluid Transport and Pore Structure Academic, New York, 1991. 6 E. W. Washburn, Proc. Natl. Acad. Sci. U.S.A. 7, 115 1921. 7 W. R. Purcell, Trans. AIME 186, 39 1949. 8 P. Z. Wong, Methods in the Physics of Porous Media Academic, London, 1999. 9 A. J. Katz and A. H. Thompson, Phys. Rev. B 34, 8179 1986. 10 P. T. Callaghan, Aust. J. Phys. 37, 359 1984. 11 P. P. Mitra, P. N. Sen, L. M. Schwartz, and P. L. Doussal, Phys. Rev. Lett. 24, 3555 1992. 12 E. J. Fordham, S. J. Gibbs, and L. D. Hall, Magn. Reson. Imaging 12, 279 1994. 13 R. L. Kleinberg, Magn. Reson. Imaging 12, 271 1994. 14 R. G. Graham, W. M. Holmes, C. D. Panlis, and K. J. Packer, Chem. Phys. Lett. 332, 319 2000. 15 H. H. Yuan and B. F. Swanson, SPE Form. Eval. 5, 17 1989. 16 W. B. Haines, J. Agric. Sci. 20, 97 1930. 17 J. C. Melrose, Can. J. Chem. Eng. 48, 638 1970. 18 J. C. Melrose, SPEJ Sept. 5, 259 1965. 19 J. C. Melrose and C. F. Brander J. Can. Pet. Technol. Oct. 13, 54 1974. 20 J. P. Heller, Proc. Soil Sci. Soc. of America 32, 778 1968. 21 A. W. Adamson, Physical Chemistry of Surfaces, Third Edition Wiley, New York, 1976. 22 Y.-Q. Song, S. Ryu, and P. N. Sen, Nature London 406, 178 2000. 23 P. T. Callaghan, Principles of Nuclear Magnetic Resonance Microscopy Oxford University Press, New York, 1993. 24 R. J. S. Brown and P. Fantazzini, Phys. Rev. B 47, 14823 1993. 25 G. C. Borgia, R. J. S. Brown, and P. Fantazzini, Phys. Rev. E 51, 2104 1995. 26 E. L. Hahn, Phys. Rev. 80, 580 1950. 27 N. V. Lisitza and Y.-Q. Song, J. Chem. Phys. 114, 9120 2001. 28 Y.-Q. Song, Magn. Reson. Imaging 19, 417 2001.

rocks,3 large pores are often observed to form a contiguous space around several grains, although extensive shape analysis was not reported. We would like to note that our use of the 2D sections is quite different from that of stereology which reconstructs 3D pores from 2D sections subject to certain geometrical models for pores.5 In this work, pore shape is derived from physical bulk measurements instead of being a prior assumption. Although the thin-section micrograph shown in Fig. 4 is representative of the many images obtained on this sample, the total number of pores observed in all images is nevertheless low, compared to bulk measurements such as mercury intrusion and DDIF. The potential under representation of the 2D pore shape in our present work will be addressed by extensive image analysis of thin-section micrographs in the future.
CONCLUSIONS

In conclusion, our combined measurements of CRMI, DDIF, and thin-section imaging have quantied the geometrical characteristics of pores, such as the pore sizes, pore shape, and pore connectivity. These quantitative analysis of pore geometry will provide a great opportunity for a deeper understanding of multi-phase ow in porous media, such as permeability and residue oil saturation of rocks.
1

B. P. Flannery, H. W. Deckman, W. G. Roberge, and K. L. DAmico, Science 237, 1439 1987. 2 J. T. Fredrich, B. Menendex, and T. F. Wong, Science 268, 276 1995. 3 ol, N. Martys, J. Olson, T. S. F. M. Auzerias, J. Dunsmuir, B. B. Ferre

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