Formation Damage Caused by Improper Mn3O4-Based Filter-Cake-Cleanup Treatments

Abstract

Summary Cleanup of filter cake is a difficult task and becomes more challenging when dealing with weighting materials [e.g., manganese tetraoxide (Mn3O4)]. Mn3O4 is a strong oxidizing agent and can be used as a catalyst because of its active phase, a nonstoichiometric Mn3O4 composed of an octahedral Mn2O3 phase and a tetrahedral MnO phase, which will result in complex interactions with most cleaning fluids. The reaction of selected organic acids and chelating agents with Mn3O4 particles as a function of time and temperature was studied. Solubility and compatibility tests of Mn3O4 particles with cleaning fluids were conducted using a high-pressure/hightemperature (HP/HT) see-through cell. Reaction kinetic tests were conducted using a three-neck round-bottom flask. Atomic absorption was used to measure manganese concentration, and X-ray diffraction was used to analyze solids remaining after the reaction. A white precipitate of manganese citrate was produced following the reaction of citric acid with Mn3O4 up to 284°F. The amount of precipitate was increased with temperature and initial acid concentration. An amino polycarboxylic acid chelating agent derived from L-glutamic acid (GLDA) (a chelant) reacted with Mn3O4 particles completely at 190°F. However, a large amount of a white was precipitate produced. Similarly, a white precipitate was observed with oxalic and tartaric acids. The reaction of diethylene triamine pentaacetic acide (DTPA) (a chelate) with Mn3O4 particles in a glass reactor produced Mn (silicates) at 212 and 284°F. The results of the present study will help drilling/completion engineers avoid using such cleaning fluids to prevent formation damage after filter-cake-removal treatments.