Reaction of Calcite and Dolomite with In-Situ Gelled Acids, Organic Acids, and Environmentally Friendly Chelating Agent (GLDA)

Well stimulation is the treatment remedy when oil/gas productivity decreases to unacceptable economical limits. Well stimulation can be carried out through either "Matrix Acidizing" or fracturing with both "Hydraulic Fracturing" and "Acid Fracturing" techniques. "Matrix Acidizing" and "Acid Fracturing" applications involve injecting an acid to react with the formation and dissolve some of the minerals present and recover or increase the permeability. The permeability enhancement is achieved by creating conductive channels "wormholes" in case of "Matrix Acidizing" or creating uneven etching pattern in case of "Acid Fracturing" treatments.

In both cases, and to design a treatment successfully, it is necessary to determine the distance that the live acid will be able to penetrate inside the formation, which in turn, determines the volume of the acid needed to carry out the treatment. This distance can be obtained through lab experiments, if formation cores are available, or estimated by modeling the treatment. The successful model will depend on several chemical and physical processes that take place including: the acid transport to the surface of the rock, the speed of the reaction of the acid with the rock, which is often referred to as "Reaction Rate", and the acid leak-off. The parameters describing these processes such as acid diffusion coefficient and reaction kinetics have to be determined experimentally to ensure accurate and reliable modeling.

Hydrochloric acid and simple organic acids such as acetic and citric acids have been used extensively for stimulation treatments. The diffusion and reaction kinetics of these acids, in a straight form, were investigated thoroughly in literature. However, solely these acids are used in a simple form in the field. Acid systems such as gelled, crosslinked gelled, surfactant-based, foam-based, or emulsified acids are used to either retard the reaction rate or to enhance acid diversion. Literature review shows that additional work is needed to understand the reaction and report the diffusion and kinetics of these systems with carbonate. In addition, a new chelating agent (GLDA) was recently introduced as a stand-alone stimulating fluid. The kinetics and the mass transfer properties of this acid were not studied before.

Therefore, the objective of this work is to study the reaction of different acid systems with calcite and dolomite and report the mass transport and kinetic data experimentally. Lactic acid, a chelating agent (GLDA), and in-situ gelled HCl-formic acids were investigated in this study. In some cases, rheology measurements and core flood experiments were conducted. The data were combined with the reaction study to understand the behavior of these acids and examine their efficiency if injected in the formation.