Because of the highly complicated nature of the interactions of solid minerals and aqueus solution in geological porous media, it is most convenient to facilitate appropriate geochemical models for the analysis of the potential chemical interactions and formation damage affects. A typical example of such studies has been carried out by Schneider (1997) in an effort to quantify the potential formation damage problems, which would result from the invasion of incompatible foreign water, such as by drilling and workover fluids and water flooding, into the Lower Spraberry sandstone reservoir formation of Texaco's Jo Mill Unit (JMU) field.


Mineral Characterization and Analyses

Based on the analyses using a scanning electron microscope, electron microprobe, and x-ray diffraction, Schneider (1997) determined the properties of the sandstone as: "Fine-grained, immature sandstones that contain considerable detrital clay minerals and carbonate clasts, along with quartz, plagioclase, and minor volcanic rock fragments and K-feldspar grains. Observed accessory minerals were muscovite, glauconite, hornblende, zircon, and pyrite. Authigenic minerals are dominated by carbonate cements and filamentous lathes of pore-lining and pore-filling illite. Some authigenic chlorite and overgrowths of quartz and feldspar are also present." He reports that the formation porosities and permeabilities are in the ranges of 10-20% and 0.5 to several mD, having considerable natural fracture permeability in certain regions and possibly some systematic fractures. He reports that this sandstone formation contains 6-10 volume % illite, 1-2 volume % chlorite, and negligible amounts of kaolinite (Scott, 1988).


Typical minerals present in porous rocks and subject to dissolution in contact with aqueous phase include the various types of carbonates such as calcite, CaCO3, magnesite, MgCO3, dolomite, CaMg(CO2)2, strontianite, SrCO3, witherite, BaCO3, and siderite, FeCO3, and various types of sulfates such as anhydrite, CaSO4, gypsum, CaSO4 • 2H2O, celestine, SrSO4, and barite, BaSO4 (Schneider, 1997). Schneider (1997) points out that the kaolinite compositions remain close to the Al2Si2O5(OH)4 formula, but the illite and chlorite formulae may vary as indicated by Aja et al. (1991a,b). He considered the typical mean compositions of the Bothamsall (Pennsylvanian), Rotliegendes (Permian), and Gulf Coast illites given, respectively, by (Warren and Curtis, 1989; Kaiser, 1984):


Schneider considered the typical mean compositions of the Gulf Coast (Kaiser, 1984) and the North Sea (Curtis et al., 1984, 1985) chlorites given, respectively, by


Water Analyses

Although the analyses of the various Jo Mill Unit produced waters were available from the Inorganic Laboratory of Texaco EPTD, Schneider (1997) considered only the analyses of waters from the wells at five locations that did not make any appreciable amount of water. Therefore, for all practical purposes, these locations preserved their original water compositions. He also considered the analyses of the Mule Shoe Ranch and Canyon Reef waters that can be used for drilling and waterflooding operations. The analyses of these waters are presented in this article by Schneider (1997). Schneider (1997) used the SOLMINEQ.88 software to simulate the potential interactions and adverse affects of the formation minerals and aqueous phase. He assumed equilibrium conditions for conservative predictions of the rock-fluid interactions and water compatibility.


Saturation Index Charts

The compatibility of foreign water with the JMU reservoir connate water is investigated in this section using the saturation index charts.


Saturation Indices of the JMU Reservoir Waters

Schneider (1997) determined the saturation indices of the carbonates and sulfates, given in Table 13-2 for the JMU #7231 water using the SOLMINEQ.88 program. The saturation index values reported with positive and negative signs in Table 13-2 indicate conditions of supersaturation and under-saturation, respectively, for various minerals. The only unexpected result is the unusually low predicted siderite undersaturation of the water. However, in general, the saturation indices of the various minerals calculated by the SOLMINEQ.88 program is consistent with the mineralogy of the JMU sandstone formation. This is a further confirmation of the accuracy of the geochemical model (Schneider, 1997).


Mixing Paths on the Mineral Stability Charts

Effects of mixing foreign and reservoir waters on mineral stability are best realized by constructing mixing paths on the mineral stability charts. Schneider (1997) investigated the compatibility of the JMU #7231 well connate water with the Mule Shoe Ranch and Canyon Reef waters considered for potential use in drilling and/or water flooding operations. The analyses of these waters are given by Schneider (1997) in Table 13-1. It is apparent that the Mule Shoe water has a higher CO2-21 and


HCO-3 content and, therefore, higher alkalinity than the other waters reported in Table 13-1. He used the SOLMINEQ.88 program and simulated the consequences of mixing the JMU #7231 connate water with 10% volume increments of the Mule Shoe Ranch and Canyon Reef waters. Schneider (1997) constructed an illite-chlorite mineral stability chart based on the following reaction equation with proper stoichiometric coefficients for the Rotliegendes illite formula:


He then plotted the curves for mixing the JMU connate water with the Mule Shoe water on this chart for the 8.4, 9.5, and 10.5 pH values He also investigated the effect of the K+ activity on the illite stability. The mixing curves for 0, 2 and 5 weight % KCl solutions at the 10.5 pH level are shown in this article, B, and C, respectively. Clearly, adding KCl increases the illite stability. However, K+ activity has a relatively smaller effect than pH.


Saturation Index Charts for Clay Minerals

Schneider (1997) constructed the illite saturation index curves for mixing the Mule Shoe water with the JMU connate water as a function of the volume percent Mule Shoe water in the mixture. For this purpose, he considered the following dissolution/precipitation reaction for the Rotliegendes illite formula:


He explains that the Mule Shoe Ranch water is usually treated with lime and therefore its pH is above 10. A comparison of A and B reveals that injecting a high pH Mule Shoe Ranch water into the reservoir reduces the illite stability of the JMU connate water upon mixing. Schneider (1997) indicate that adding KCl into the Mule Shoe Ranch water improves the illite stability.


Activity-Activity Charts

Schneider (1997) equilibrated the activities of the five connate water compositions given in Table 13-1 to the 135°F temperature of the Jo Mill Unit reservoir using the SOLMINEQ.88 program. He then plotted these activity values on the activity-activity charts. All points appear inside the mineral stability fields of the types of clay minerals present in the sandstone formation of the Jo Mill Unit reservoir. Hence, this confirmed the validity of the geo-chemical model and the accuracy of the mineral stability field charts generated by the SOLMINEQ.88 program. Schneider (1997) explains that the formula


of the Rotliegendes illite is somewhat similar to the formula KA12 (AlSi3]Olo(OH)2 of the muscovite, which is an end-member composition illite. Because the JMU reservoir contains a high amount of illite (6-10 volume %), the JMU reservoir connate water compositions should appear within the muscovite stability region by Schneider (1997). Schneider (1997) constructed the illite-chlorite mineral stability charts shown in this article based on the following illite to chlorite incongruent reactions using the proper stoichiometric coefficients according to the compositional formulae of the illites and chlorites mentioned above:


Again, as indicated by the mineral stability charts shown in this article by Schneider (1997), all the JMU reservoir connate water composition appear inside the mineral stability regions of the illites. Schneider (1997) constructed the illite-kaolinite mineral stability charts shown in this article based on the following illite to kaolinite incongruent reactions using a proper set of stochiometric coefficients according to the compositional formulae of the illites and kaolinites considered for the study:


Because of the existence of a large quantity of illite (6-10 volume %) and a negligible amount of kaolinite in the JMU sandstone reservoir formations, all the JMU connate waters appear inside the illite stability region. Schneider (1997) constructed the chlorite-kaolinite mineral stability charts shown in this article the following chlorite to kaolinite incongruent reactions using the proper set of stoichiometric coefficients according to the compositional formulae of the chlorites considered for the study


Because of a relatively larger quantity of the chlorite (1-2 volume %) compared to the negligible amount of kaolinite present in the JMU sandstone formation, all the JMU connate waters appear inside the chlorite stability region.


References

Aja, S. U., Rosenberg, P. E., & Kittrick, J. A., "Illite Equilibria in Solutions: I. Phase Relationships in the System K2O-Al2O3-SiO2-H2O between 25 and 250°C," Geochimica et Cosmochimica Acta, Vol. 55, 1991a, pp. 1353-1364.

Aja, S. U., Rosenberg, P. E., & Kittrick, J. A., "Illite Equilibria in Solutions: II. Phase Relationships in the System K2O-MgO-Al2O3-SiO2-H2O," Geochimica et Cosmochimica Acta, Vol. 55, 1991b, pp. 1365-1374.

Amaefule, J. O., Kersey, D. G., Norman, D. L., & Shannon, P. M., "Advances in Formation Damage Assessment and Control Strategies," CIM Paper No. 88-39-65, Proceedings of the 39th Annual Technical Meeting of Petroleum Society of CIM and Canadian Gas Processors Association, June 12-16, 1988, Calgary, Alberta, 16 p.

Basset, R. L., & Melchior, D. C., "Chemical Modeling of Aqueous Systems—An Overview," Chapter 1, pp. 1-14, in Chemical Modeling of Aqueous Systems II, Melchoir, D. C. & Basset, R. L. (Eds.), ACS Symposium Series 416, ACS, Washington, 1990.

Bertero, L., Chierici, G. L., Gottardi, G., Mesini, E., & Mormino, G., "Chemical Equilibrium Models: Their Use in Simulating the Injection of Incompatible Waters," SPE Reservoir Engineering Journal, February 1988, pp. 288-294.

Bethke, C. M., Geochemical Reaction Modeling, Concepts and Application, Oxford University Press, New York, 1996, 397 p.

Bj0rkum, P. A., & Gjelsvik, N., "An Isochemical Model for Formation of Authigenic Kaolinite, K-feldspar, and Illite in Sediments," Journal of Sedimentary Petrology, Vol. 58, No. 3, 1988, pp. 506-511.

Carnahan, C. L., "Coupling of Precipitation-Dissolution Reactions to Mass Diffusion via Porosity Changes," Chemical Modeling of Aqueous Systems II, Chapter 18, pp. 234-242, D.C. Melchior & R. L. Basset (Eds.), ACS Symposium Series 416, American Chemical Society, Washington, DC, 1990.

Chang, F. F., and Civan, F., "Modeling of Formation Damage due to Physical and Chemical Interactions between Fluids and Reservoir Rocks," SPE 22856 paper, Proceedings of the 66th Annual Technical Conference and Exhibition of the Society of Petroleum Engineers, October 6-9, 1991, Dallas, Texas.

Chang, F. F., & Civan, F., "Predictability of Formation Damage by Modeling Chemical and Mechanical Processes," SPE 23793 paper, Proceedings of the SPE International Symposium on Formation Damage Control, February 26-27, 1992, Lafayette, Louisiana, pp. 293-312.

Chang, F. F., & Civan, F., "Practical Model for Chemically Induced Formation Damage," Journal of Petroleum Science and Engineering, Vol. 17, No. 1/2, February 1997, pp. 123-137.

Curtis, C. D., Ireland, B. J., Whiteman, J. A., Mulvaney, R., & Whittle, C. K., "Authigenic Chlorites: Problems with Chemical Analysis and Structural Formula Calculation," Clay Minerals, Vol. 19, 1984, pp. 471-481.

Curtis, C. D., Hughes, C. R., Whiteman, J. A., & Whittle, C. K., "Compositional Variation Within Some Sedimentary Chlorites and Some Comments on their Origin," Mineralogical Magazine, Vol. 49, 1985, pp. 375-386.

Demir, L, "Formation Water Chemistry and Modeling of Fluid-Rock Interaction for Improved Oil Recovery in Aux Vases and Cypress Formations," Department of Natural Resources, Illinois State Geological Survey, Illinois Petroleum Series 148, 1995, 60 p.

Dewers, T, Civan, E, and Atkinson, G., "Formation Damage and Carbonate Scale During Sub-Salt Petroleum Production," research proposal funded by the Interdisciplinary Research Incentive Program at the University of Oklahoma, 2000, 20 p. unpublished.

Drever, J. I., The Geochemistry of Natural Waters, Second Edition, Prentice Hall, New York City, 1988.

Dullien, F. A. L., Porous Media Fluid Transport and Pore Structure, 2nd ed., Academic Press, Inc., San Diego, 1992, 574 p.

ESTSC/COSMIC, "Geochemical Modeling of Aqueous Systems, EQ3NR," Software Technology Transfer, Energy Science and Technology Software Center (ESTSC), Oak Ridge, TN, and NASA Computer Software Technology Transfer Center (COSMIC), the University of Georgia, Athens, GA, Vol. 1, No. 1, Winter 1993, p. 17.

Fletcher, P., Chemical Thermodynamics for Earth Scientists, Longman Group UK Ltd., London, 1993.

Glover, M. C., & Guin, J. A., "Dissolution of a Homogeneous Porous Medium by Surface Reaction," AIChE Journal, Vol. 19, No. 6, November 1973, pp. 1190-1195.

Haggerty, D. J., & Seyler, B., "Investigation of Formation Damage from Mud Cleanout Acids and Injection Waters in Aux Vases Sandstone Reservoirs," Department of Natural Resources, Illinois State Geological Survey, Illinois Petroleum Series 152, 1997, 40 p.

Hayes, M. J., & Boles, J. R., "Volumetric Relations Between Dissolved Plagioclase and Kaolinite in Sandstones: Implications for Aluminum Mass Transfer in San Joaquin Basin, California," Origin, Diagenesis, and Petrophysics of Clay Minerals in Sandstones, SEPM Special Publication No. 47, 1992, pp. 111-123.

Helgeson, H. C., Brown, T. H., Nigrini, A., & Jones, T. A., "Calculation of Mass Transfer in Geochemical Processes Involving Aqueous Solutions," Geochimica Cosmochimica Acta, Vol. 34, 1970, pp. 569-592.

Holstad, A., "Mathematical Modeling of Diagenetic Processes in Sedimentary Basins," Mathematical Modelling of Flow Through Porous Media, Bourgeat, A. P., Carasso, C., Luckhaus, S., & Mikelic, A., (Eds.), World Scientific Publ. Co. Pte. Ltd., 1995, pp. 418-428.

Israelachvili, J., Intermolecular and Surface Forces, 2nd ed., Academic Press, San Diego, 1992, 450 p.

James, R. O., & Parks, G. A., "Characterization of Aqueous Colloids by their Electrical Double-Layer and Intrinsic Surface Chemical Properties," in Surface and Colloid Science, Vol. 12, Matijevic, E. (ed.), Plenum Press, New York, pp. 119-216.

Jennings, A. A., & Kirkner, D. J., "Instantaneous Equilibrium Approximation Analysis," J. of Hydraulic Eng., Vol. 110, No. 12, 1984, pp. 1700-1717.

Kaiser, W. R., "Predicting Reservoir Quality and Diagenetic History in the Frio Formation (Oligocene) of Texas," Clastic Diagenesis: AAPG Memoir 37, McDonald, D. A. & Surdam, R. C. (Eds.), American Association of Petroleum Geologists, 1984, pp. 195-215.

Kandiner, H. J., & Brinkley, S. R., "Calculation of Complex Equilibrium Relations," Ind. Eng. Chem., Vol. 42, 1950, pp. 850-855.

Kharaka, Y. K., & Barnes, I., "SOLMINEQ: Solution-mineral-equilibrium Computations: U.S. Geological Survey Computer Contributions," NTIS No. PB215-899, 1973, 81 p.

Kharaka, Y. K., Gunter, W. D., Aggarwal, P. K., Perkins, E. H., & DeBraal, J. D., "SOLMINEQ.88: A Computer Program for Geochemical Modeling of Water-Rock Interactions," U.S. Geological Survey Water-Resources Investigations Report 88-4227, Menlo Park, CA, 1988, 429 p.

Labrid, J., & Bazin, B., "Flow Modeling of Alkaline Dissolution by a Thermodynamic or by a Kinetic Approach," SPE Reservoir Engineering, May 1993, pp. 151-159.

Li, Y-H., Crane, S. D., Scott, E. M., Braden, J. C., & McLelland, W. G., "Waterflood Geochemical Modeling and a Prudhoe Bay Zone 4 Case Study," SPE Journal, Vol. 2, March 1997, pp. 58-69.

Li, Y-H., Fambrough, J. D., & Montgomery, C. T., "Mathematical Modeling of Secondary Precipitation from Sandstone Acidizing," SPE Journal, December 1998, pp. 393-401.

Lichtner, P. C., "Continuum Model for Simultaneous Chemical Reactions and Mass Transport in Hydrothermal Systems," Geochimica et Cosmochimica Acta, Vol. 49, 1985, pp. 779-800.

Lichtner, P. C., "The Quasi-Stationary State Approximation to Coupled Mass Transport and Fluid-Rock Interaction in a Porous Medium," Geochimica et Cosmochimica Acta, Vol. 52, 1988, pp. 143-165.

Lichtner, P. C., "Time-Space Continuum Description of Fluid/Rock Interaction in Permeable Media," Water Resources Research, Vol. 28, No. 12, December 1992, pp. 3135-3155.

Liu, X., Ormond, A., Bartko, K., Li, Y, & Ortoleva, P., "A Geochemical Reaction-Transport Simulator for Matrix Acidizing Analysis and Design," J. of Petroleum Science and Engineering, Vol. 17, No. 1/2, February 1997, pp. 181-196.

Liu, X., & Ortoleva, P., "A Coupled Reaction and Transport Model for Assessing the Injection, Migration, and Fate of Waste Fluids," SPE 36640 paper, Proceedings of the 1996 SPE Annual Technical Conference and Exhibition, Denver, Colorado, October 6-9, 1996, pp. 661-673.

Liu, X., & Ortoleva, P., "A General-Purpose, Geochemical Reservoir Simulator," SPE 36700 paper, Proceedings of the 1996 SPE Annual Technical Conference and Exhibition, Denver, Colorado, October 6- 9, 1996, pp. 211-222.

Melchior, D. C., & Bassett, R. L. (Eds.), "Chemical Modeling of Aqueous Systems II," ACS Symposium Series 416, American Chemical Society, Washington, DC, 1990, 556 p.

Nordstrom, D. K., & Munoz, J. L., Geochemical Thermodynamics, 2nd ed., Blackwell Scientific Publications, Boston, 1994.

Ortoleva, P., Geochemical Self-Organization, Oxford University Press, New York, 1994.

Plummer, L. N., Geochemical Modeling of Water-Rock Interaction: Past, Present, Future," in Water-Rock Interation, Vol. 1, Kharaka, Y. K. & Maest, A. S. (Eds.), 1992, Balkema, Rotterdam, Brookfield, 858 p.

Prigogine, I., & DeFay, R., Chemical Thermodynamics, D.H. Everett (trans.), Longmans Green and Co., London, 1954, 543 p.

Rege, S. D., & Fogler, H. S., "Competition Among Flow, Dissolution and Precipitation in Porous Media," AIChE J., Vol. 35, No. 7, 1989, pp. 1177-1185.

Sahai, N., & Sverjensky, D. A., "GEOSURF: A Computer Program for Modeling Adsorption on Mineral Surfaces from Aqueous Solution," Computers and Geosciences, Vol. 24, No. 9, 1998, pp. 853-873.

Schechter, R. S., & Gidley, J. L., "The Change in Pore Size Distribution from Surface Reactions in Porous Media," AIChE Journal, Vol. 15, No. 3, May 1969, pp. 339-350.

Schneider, G. W., "A Geochemical Model of the Solution-Mineral Equilibria Within a Sandstone Reservoir," M.S. Thesis, The University of Oklahoma, 1997, 157 p.

Scott, A. R., "Organic and Inorganic Geochemistry, Oil-Source Rock Correlation, and Diagenetic History of the Permian Spraberry Formation, Jo Mill Field, Northern Midland Basin, West Texas," M.S. Thesis, Sul Ross State University, Alpine, Texas, 1988.

Sears, S. O., & Langmuir, D., "Sorption and Mineral Equilibria Controls on Moisture Chemistry in a C-Horizon Soil," Journal of Hydrology, Vol. 56, 1982, pp. 287-308.

Shaughnessy, C. M., & Kline, W. E., "EDTA Removes Formation Damage at Prudhoe Bay," SPE 11188 paper, presented at the SPE Annual Technical Conference and Exhibition, New Orleans, Louisiana, September 26-29, 1982.

Shaughnessy, C. M., & Kline, W. E., "EDTA Removes Formation Damage at Prudhoe Bay," Journal of Petroleum Technology, October 1983, pp. 1783-1792.

Steefel, C. I., & Lasaga, A. C., "Evolution of Dissolution Patterns- Permeability Change Due to Coupled Flow and Reaction," Chemical Modeling of Aqueous Systems II, Chapter 16, pp. 212-225, D.C. Melchior & R. L. Basset (Eds.), ACS Symposium Series 416, American Chemical Society, Washington, DC, 1990.

Stumm, W., & Morgan, J. J., Aquatic Chemistry: Chemical Equilibria and Rates in Natural Waters, John Wiley and Sons, New York, New York, 1996.

Todd, A. C., & Yuan, M. D., "Barium and Strontium Sulfate Solid Solution Formation in Relation to North Sea Scaling Problems," SPE 18200 paper, Proceedings of the Society of Petroleum Engineers 63rd Annual Technical Conference and Exhibition, Houston, Texas, October 2-5, 1988, pp. 193-198.

Walsh, M. P., Lake, L. W, & Schechter, R. S., "A Description of Chemical Precipitation Mechanisms and Their Role in Formation Damage During Stimulation by Hydrofluoric Acid," Journal of Petroleum Technology, September 1982, pp. 2097-2112.

Warren, E. A., & Curtis, C. D., "The Chemical Composition of Authigenic Illite Within Two Sandstone Reservoirs as Analysed by TEM," Clay Minerals, Vol. 24, 1989, pp. 137-156.

Westall, J. C., "Reactions at the Oxide-Solution Interface: Chemical and Electrostatic Models," in Geochemical Processes at Mineral Surfaces, Davis, J. A. & Hayes, K. F. (Eds.), ACS, Washington, 1986, pp. 54-78.

Yates, D. E., Levine, S., & Healy, T. W., "Site-Binding Model of the Electrical Double Layer at the Oxide/Water Interface," Journal of the Chemical Society Fraday Transactions /, Vol. 70, 1974, pp. 1807-1818.

Yeboah, Y. D., Somuah, S. K., & Saeed, M. R., "A New and Reliable Model for Predicting Oilfield Scale Formation," SPE 25166 paper, Proceedings of the SPE International Symposium on Oilfield Chemistry, New Orleans, Louisiana, March 2-5, 1993, pp. 167-176.