Secondary Recovery - Carbon Dioxide Solvent Flooding for Increased Oil Recovery

The presence of gypsum in samples subjected to standard core analysis introduces serious errors in the measurement of water saturation and porosity. The magnitude of these errors, depending upon the type of analysis procedure used, has been evaluated experimentally and theoretically. Water-saturated pore volumes determined by vacuum distillation or retort procedures may be too high by as much as 48 per cent of the volume of gypsum present. The maximum error in this value determined by Dean-Stark extraction with toluene is 36 per cent of the gypsum volume. If pore space is measured by a Boyle's law type porosimeter the maximum erorr due to gypsum is 38 per cent of the original gypsum volume present. The conscientious core analyst may eliminate the errors caused by gypsum by either of two methods. He may apply suitable corrections for the water of crystallization removed from gypsum, or take special precautions to prevent dehydration of gypsum during core cleaning and alzalysis procedures. These alternatives are discussed and methods for obtaining reliable core analysis data are proposed. Gypsum (CaSO4 . 2H2O) occurs as a common mineral in many of the world's sedimentary basins. In addition to its presence as primary bedded evaporitic deposits, it is often found as secondary replacement zones and pore-fillings in host rocks. That it may cause false indications in porosity, both on neutron logs and in standard core analysis, has been generally recognized. False porosity interpretations from neutron logs result because the chemically bound water in gypsum attenuates neutrons as effectively as free water. Errors in core analysis result when gypsum is dehydrated prior to or during the analysis. Vacuum retort procedures used by many laboratories to determine fluid saturation and porosity effect a complete removal of water of crystallization from gypsum. The crystal water, distilled and collected with free water from the sample, is counted as water-sat11rated pore space. Dehydration of gypsum results in a decrease in volume occupied by calcium sulfate and a corresponding increase in pore volume. Thus, if gypsum is dehydrated by sample cleaning and drying procedures, subsequent porosity measurements with gas expansion or compression instruments will be high. The qualitative effect of gypsum on porosity determinations by retort procedures was discussed in a recent article by Bynum and Koepl3. They concluded that since false porosity was interpreted as being water saturated, determinations of oil content were not affected. Others in the industry, however, have pointed out that porosity values are often used with values of water saturation determined independently, e.g., from electric resistivity logs in making reserve estimates. Values of water saturation calculated from the formation resistivity using the Archie equation, S4= are actually low if values of are high due to gypsum. In this case, false porosity values due to gypsum could cause serious errors in calculations of oil-in-place. This investigation was made to determine quantitatively the effect of gypsum on porosity values determined by different core analysis procedures. EXPERIMENTAL PROCEDURES Dehydration of Gypsum The extent and rate of removal of water of crystallization from gypsum under conditions encountered in core analysis procedures were studied. Taken for the experiments were three types of relatively pure, naturally occurring gypsum, viz. selenite, satin spar and massive gypsum. Although all samples probably contained trace chemical impurities, each type lost the theoretical amount of water upon complete dehydration. An automatic recording thermobalance, similar to one described by Mauer2, was used to obtain dehydration rate data for samples heated in dry air. Water