Flowback Additive for Acidizing Fluid to Stimulate Carbonate Gas Reservoirs
Authors: Saini Rajesh K. , Sayed Mohammed A. , Cairns Amy J. 
Published: June 2024

Acidizing of oil- and gas-bearing carbonate reservoirs is generally undertaken by using strong mineral acids such as hydrochloric acid (HCl) to enhance permeability. One of the major challenges associated with HCl injection is tuning the reactivity profile to favor the transport of live acid deep into the reservoir while achieving a minimum rock face dissolution. The mineral acid is therefore emulsified in a hydrocarbon phase (e.g., diesel) to retard its reactivity with the rock matrix. The use of emulsified acid is hindered by several limitations such as low emulsion stability at high temperatures, pumping limitations due to high viscosity, the potential of formation damage, and cumbersome mixing procedures at the field scale. In addition, the brines formed as a result of this reaction can be difficult to produce due to higher density and capillary pressures, unfavorable wettability, and low formation pressure. Here, we report on the development of dual-purpose additives that were specifically designed to enhance the recovery of high-density brines and retard the acid/rock reactivity upon addition to the stimulation treatment.

Accordingly, seven new additives with fluid flowback properties were developed for use in a single-phase acidizing fluid consisting of HCl (15 wt% and 28 wt%) with the required additives, such as corrosion inhibitor and intensifier, and H2S scavenger. The flowback enhancers (FBEs) were formulated from a blend of water, ester or terpene solvents, alcohols, and surfactants to form optically clear nano- and microemulsions. Surfactant selection was driven by the need to exhibit demulsification properties with condensate, high chemical and thermal stability, compatibility in strongly acidic media, and high-density brines under harsh reservoir conditions. To assess the FBE performance in acidizing formulations (i.e., to serve as both an FBE and retarder), screening studies consisting of static rock dissolution tests and surface tension measurements were performed to downselect FBEs suitable for this application. This was coupled with brine displacement tests in addition to compatibility and stability studies. FBEs that demonstrated superior performance were then selected for further evaluation under reservoir conditions [i.e., core flow matrix acidizing to measure regained permeability and computed tomography (CT) scan for analyzing the wormhole propagation].

The droplet size of the as-prepared nano- and microemulsions was found to be between 10 nm and 850 nm. The FBEs formulated in this study were found to prevent emulsion formation in the presence of condensate and demonstrated remarkable chemical and thermal stability in concentrated acid at temperatures up to 300°F for a duration of up to 24 hours, as confirmed by the consistent low surface tension values (21–29 mN/m). With regard to fluid displacement, column tests performed under ambient conditions revealed quick brine displacement with recovery exceeding 75 vol% in comparison with 16 vol% in the absence of the FBE. Interestingly, the addition of a select FBE from this study to 28 wt% HCl was found to retard the reaction of carbonate dissolution at room temperature. This led us to assess the performance under reservoir conditions utilizing core flow testing. Accordingly, the addition of FBE-F to 28 wt% HCl led to an improvement in permeability by up to 267% as compared with 15% without FBE added. These results are further supported by the CT scan images of the acidized cores, which revealed the formation of a deeper wormhole in the presence of a select FBE.