Producing-Equipment, Methods and Materials - An Improved Acid for Calcium Sulfate-Bearing Formations

An improved acid for the treatrrzent of sulfate-con-raining limestones and dolomites is described. The acid is designed to reduce he reprecipitation of dissolved calcium sulfate and the possibility of plugging permeable flow channels. In addition, this improved acid has a much lower reaction rate than that of regular acid; the advantages of a "retarded" acid are obtainable. Field testing of the acid has shown it suitable for use in sulfate-containing formations. Substantial improvements in productivity generally resulted. INTRODUCTION Acid treatments of limestones, dolomites and other formations bearing carbonate deposits are frequently unsuccessful when the calcareous formation contains sulfate, either as anhydrite (CaSO,) or gypsum (CaSO4. 2H2O). Preliminary dissolution in acid followed by redeposition of calcium sulfate appears to be a major factor contributing to poor well performance after acidizing. The precipitate is usually the gypsum form of calcium sulfate, but in higher temperature formations it may be anhydrite. The freshly precipitated crystals are nearly always very small and needle-like. They may occupy a gross volume many times that of the original anhydrite crystals and will obviously constitute an impediment to flow through newly enlarged flow channels. It is believed that the redeposition problem is most severe when anhydrite lines the fracture systems and large pores which supply the effective permeability of a formation. Microscopic inclusions of calcium sulfate also present large sulfate surface areas for dissolution in acid. In either case, great amounts of calcium sulfate may dissolve before the acid can be spent on formation carbonates. For regular spent acid (originally 15 per cent hydrochloric acid) the precipitate could be as much as 270 Ib gypsum/1000 gal acid. Two techniques have been applied by the industry for reducing sulfate plugging during acidizing. The method'.' commonly employed in the field is the attempted removal of a quantity of regular treating acid before it has reacted completely with the formation. This is practiced because the solubility of calcium sulfate is greater in a solution that is still acidic than in one which has been largely spent on the formation rock. The chance of precipitative plugging is therefore reduced if the withdrawal is successful. However, it is often impossible to get the acid out of the formation before precipitation occurs. A second possible method, which at first glance appears practical, involves addition to the acid of sequestering agents which form strong soluble complexes with calcium ions. These chemicals do increase the "solubility" of calcium sulfate in fresh acid, but to a lesser extent in spent acid. The sequestering agents have, therefore, proved unsatisfactory because the amount of sulfate eventually deposited from the spent acid may be greater than that from regular acid. Another logical approach to the problem of calcium sulfate reprecipitation is the prevention of the initial dissolution of calcium sulfate by the common ion effect. This may be accomplished by adding a soluble calcium salt to the fresh acid. The use of calcium salts in treating acids is not entirely new. An earlier suggested use of a soluble calcium salt in hydrochloric acid apparently failed to recognize the full extent to which the solubility of calcium sulfate could be suppressed. The present study extends this earlier work and adds certain improvements toward the development of a practical anti-anhydrite acid. LABORATORY DEVELOPMENT Calcium Sulfate Solubility Table 1 shows the results of a laboratory study performed to establish the effect of calcium chloride concentration on gypsum solubility. Because of the strong tendency of calcium sulfate to form supersaturated solutions, accurate solubilities are difficult to determine. These solubility data probably are reliable to within ± 15 per cent. The solubility of calcium sulfate in 15 weight per cent hydrochloric acid increases with increasing temperature. This trend is also followed in hydrochloric acid which cantains calcium chloride. This is contrary to the solubility behavior of calcium sulfate in water, wherein the solubility decreases with increasing temperature.