Comparison of Wormhole Profiles on Carbonate Rocks Using Emulsified and Single-Phase Retarded Acids

Acid retardation through emulsification is commonly used in reservoir stimulation operations, however, emulsified acid are viscous fluids, thus require additional equipment at field for preparation and pumping requirements. Mixture of HCl with organic acids and/or chemical retarders have been used developed to retard acid reaction with carbonate, however, lower dissolving power. Development of low viscosity and high dissolving retarded acid recipes (e.g., equivalent to 15-26 wt.% HCl) addresses the drawbacks of emulsified acids and HCl acid mixtures with weaker organic acids. The objective of this study is to compare wormhole profile generated as a result of injecting acids in Indian limestone cores using 28 wt.% emulsified acid and single-phase retarded acids at comparable dissolving power at 200 and 300°F. Coreflood analysis testing was conducted using Indiana limestone core plugs to assess the pore volume profile of retarded acid at temperatures of 200 and 300° F. This test is supported by Computed Tomography to evaluate the propagation behavior as a result of the fluid/rock reaction. Wider wormholes were observed with 28 wt.% emulsified acid at 200°F when compared to test results conducted at 300°F. The optimum injection rate was 1 cm3/min at 200 and 300°F based on wormhole profile and examined flow rates. Generally, face-dissolution and wider wormholes were observed with emulsified acids, especially at 200°F. Narrower wormholes were formed as a result of injecting retarded acids into Indiana limestone cores compared to 28 wt.% emulsified acid. Breakthrough was not achieved with retarded acid recipe at 300°F and flow rates of 1 and 3 cm3/min, suggesting higher flow rates (e.g., > 3 cm3/min) are required for the retarded acid to be more effective at 300°F.

A Matrix Acidizing System for Controlled Carbonate Well Stimulation using a Carboxylic Acid Salt with a Chelating Agent

This work presents a matrix acidizing formulation which comprises a salt of monochloroacetic acid giving a delayed acidification and a chelating agent to prevent precipitation of a calcium salt. Results of dissolution capacity, core flood test and corrosion inhibition are presented and are compared to performance of 15 wt% emulsified HCl. Dissolution capacity tests were performed in a stirred reactor at atmospheric pressure using equimolar amounts of the crushed limestone and dolomites. Four different chelating agents were added to test the calcium ion sequestering power. Corrosion tests were executed using an autoclave reactor under nitrogen atmosphere at 10 barg. Core flood tests were performed to simulate carbonate matrix stimulation using limestone cores. It was found that the half-life time of the hydrolysis reaction is 77 min at a temperature of 100 °C. Sodium gluconate and the sodium salt of D-glucoheptonic acid were identified to successfully prevent the precipitation of the reaction product calcium glycolate at a temperature of 40 °C. Computed Tomography (CT) scans of the treated cores at optimum injection rate showed a single wormhole formed. At 150 °C an optimum injection rate of 1 ml/min was found which corresponds to a minimum PVBT of 6. In addition, no face dissolution was observed after coreflooding. Furthermore, the corrosion rates of different metallurgies (L80 and J55) were measured which are significantly less than data reported in literature for 15wt% emulsified HCl. The novelty of this formulation is that it slowly releases an organic acid in the well allowing deeper penetration in the formation and sodium gluconate prevents precipitation of the reaction product. The corrosivity of this formulation is relatively low saving maintenance costs to installations and pipe work. The active ingredient in the formulation is a solid, allowing onsite preparation of the acidizing fluid.

Optimum Injection Rate of A New Chelate That Can Be Used To Stimulate Carbonate Reservoirs

Summary Different chelating agents were used as alternatives for hydrochloric acid (HCl) in matrix acidizing to create wormholes in carbonate formations. Previous studies demonstrated the use of ethylenediaminetetraacetic acid (EDTA), hydroxy ethylenediaminetriacetic (HEDTA), and glutamic acid-N,N-diacetic acid (GLDA) as standalone stimulation fluids to stimulate carbonate reservoirs. The main problem of using EDTA and HEDTA is their low bio-degradability. GLDA was introduced as a standalone stimulation fluid for deep carbonate reservoirs where HCl can cause corrosion and face dissolution problems. In this study, calcite cores 1.5 in. in diameter and 6 or 20 in. in length were used to determine the optimum conditions where the GLDA can break through the core and form wormholes. GLDA solutions with pH values of 1.7, 3, and 3.8 were used. The optimum conditions of injection rate and pH were determined using coreflood experiments. Damköhler number was determined using the wormhole length and diameter from the CT scan 3D and 2D images. GLDA was compared with chelates that are used in the oil industry such as EDTA and HEDTA. GLDA also was used to stimulate parallel cores with different permeability ratios (up to 6.25). GLDA was found to be very effective in creating wormholes at pH = 1.7, 3, and 3.8; at different injection rates; and at temperatures up to 300°F. Increasing the temperature increased the reaction rate and less volume of GLDA was required to break through the core and form wormholes. Unlike HCl, in GLDA there was no face dissolution or washout in the cores even at low injection rates (0.5 cm3/min). An optimum injection rate and Damköhler number were found at which the pore volume (PV) required to create wormholes was the minimum. GLDA at pH 1.7 and 3 created wormholes with a small number of PV (at 1 cm3/min, GLDA at pH 1.7 required 1.5 PV at 300°F, and at pH 3 it required 1.8 PV). Compared with acetic acid, the volume of GLDA at pH 3 required to create wormholes was less than that required with acetic acid at the same conditions. GLDA was found to be effective in stimulating parallel cores up to 6.25 permeability contrast (final permeability/initial permeability).