Iron precipitation during matrix acidizing treatments is a well-known problem. During matrix acidizing, successful iron control can be critical to the success of the treatment. Extensive literature review highlighted that no systematic study was conducted to determine where this iron precipitates, the factors that affect this precipitation, and the magnitude of the resulting damage. Iron (III) precipitation occurs when acids are spent and the pH rises above 1, which can cause severe formation damage. Chelating agents are used during these treatments to minimize iron precipitation. Disadvantages of currently used chelating agents include limited solubility in strong acids, low thermal stability, and/or poor biodegradability. In this study, different factors affecting iron precipitation in Indiana limestone rocks were examined. Two chelating agents, GLDA and HEDTA, were tested at different conditions to assess their iron control ability. Results show that a significant amount of iron precipitated, producing a minimal or no gain in the final permeability, this indicated severe formation damage. The damage increased with the increase of the amount of iron in solution. When chelating agents were used, the amount of iron recovered depended on both chelate-to-iron mole ratio and the initial permeability of the cores. Calcium is chelated along with iron, which limits the effectiveness of chelating agents to control iron (III) precipitation. Acid solutions should be designed considering this important finding for more successful treatments.

It has been a practice to use seawater for preparing acid in offshore operations where fresh water is relatively expensive or logistically impossible to use. However, hydrochloric acid will release calcium ion into solution, which will combine with sulfate ion in seawater (greater than 3000 ppm) and calcium sulfate will precipitate once it exceeds its critical scaling tendency. A few studies have provided evidence for this problem and how to address this problem has not been fully examined. Core flood tests were conducted using Austin Chalks cores (1.5 in. x 6 in. and 1.5 in. x 20 in.) with permeability 5 md to investigate the effectiveness of scale inhibitor. A synthetic seawater was prepared according to the composition of seawater in the Arabian Gulf. Calcium, sulfate ions, and scale inhibitor concentrations were analyzed in the core effluent samples. Solids collected in the core effluent samples were analyzed using X-ray photoelectron spectroscopy (XPS) technique and thermodynamic calculation using OLI Analyzer software were conducted to identify the critical scaling tendency of calcium sulfate at different temperatures. Results showed that calcium sulfate precipitation occurred when seawater was used in any stage during matrix acidizing including preflush, post-flush, or in the main stage. Injection rate was the most important parameter that affected calcium sulfate precipitation; permeability reduction was significant at low flow rates, while at high rates wormhole breakthrough reduced the severity of the problem. More CaSO4 precipitated at high temperatures, accounting for more significant permeability reduction in the cores. The values of critical scaling tendency at various temperatures calculated by OLI ScaleChem 4.0.3 were believed to be 2.1, 2.0, and 1.2 respectively. A scale inhibitor (a sulfonated terpolymer) was found to be compatible with hydrochloric acid systems and can tolerate high concentration of calcium (30,000 mg/l). Analysis of core effluent indicated that the new treatment successfully eliminated calcium sulfate scale deposition. The concentration of scale inhibitor ranged from 20 to 250 ppm, depending on the scaling tendencies of calcium sulfate. This work confirms the damaging effect of preparing hydrochloric acid solutions using seawater on the permeability of carbonate cores. Therefore, it is recommended to use fresh water instead of seawater to prepare HCl acids whenever possible. If fresh water is not available, then a proper scale inhibitor should be added to the acids to avoid calcium sulfate precipitation.

Carbonate reservoirs are heterogeneous; therefore, proper acid placement/diversion is required to make matrix acid treatments effective. Viscoelastic surfactants (VES) are used as diverting agents in carbonate matrix acidizing. However, these surfactants can adversely affect wettability around the wellbore area. Lab and field studies show that significant amounts of VES are retained in the reservoir, even after an EGMBE postflush. Optimizing acid treatments requires a study of the effect of VES on wettability. In a previous study using contact angle experiments, it was reported that spent acid solutions with VES only, and with VES and EGMBE are water-wetting. In this thesis, we studied the effect of two amphoteric amine-oxide VES', designated as "A" and "B" on the wettability of Austin cream chalk using contact angle experiments. We extended the previous study by using outcrop rocks prepared to simulate reservoir conditions, by demonstrating that VES adsorbs on the rock using two-phase titration experiments, by studying the effect of temperature on wettability and adsorption, and by developing a detailed procedure for contact angle experiments. We found that for initially oil-wet rocks, simulated acid treatments with VES "A" and "B" diversion stages and an EGMBE preflush and postflush made rocks water-wet at 25, 80, and 110 degrees C. Simulated acid treatments with a VES "A" diversion stage only made rocks water-wet at 25 degrees C. Our results suggest that both VES formulations cause a favorable wettability change for producing oil. The two-phase titration experiments show that both VES "A" and "B" adsorb on the rock surface. From our literature review, many surfactant wettability studies use contact angle measurements that represent advancing contact angles. However, wettability during stimulation is represented by receding contact angles. Results of static receding contact angles may be misinterpreted if low oil-acid IFT's cause oil droplets to spread. Spreading could be a reflection of the effect of the surfactants on the fluid-fluid interface rather than the rock-fluid interface. The new procedure shows the effect of VES and EGMBE on the rock-fluid interface only, and so represents the actual wettability.

Viscoelastic surfactant have found numerous application in the oil fields as fracturing and matrix acidizing fluid additives in the recent years. They have the ability to form long worm-like micelles with the increase in pH and calcium concentration, which results in increasing the viscosity and elasticity of partially spent acids. On one hand, concentration of surfactant in the fluids has profound effects on their performance downhole. Additionally, there is continuous debate in the industry on whether the gel generated by these surfactants causes formation damage, especially in dry gas wells. Therefore, being able to analyze the concentration of these surfactants in both live and spent acids is of great importance for production engineers who apply surfactant-based fluids in the oil fields. In the present work, a two-phase titration method was optimized for quantitative analysis of a carboxybetaine viscoelastic surfactant, and surfactant retention in calcite cores was quantitatively determined by two phase titration method and the benefits of using mutual solvents to break the surfactant gel formed inside the cores was assessed. On the other hand, high temperatures and low pH are usually involved in surfactant applications. Surfactants are subjected to hydrolysis under such conditions due to the existence of a peptide bond (-CO-NH-) in their molecules, leading to alteration in the rheological properties of the acid. The impact of hydrolysis at high temperatures on the apparent viscosity of carboxybetaine viscoelastic surfactant-based acids was evaluated in the present study, and the mechanism of viscosity changes was determine by molecular dynamics (MD) simulations. Our results indicate that, first, significant amount of surfactant has been retained in the carbonate matrix after acidizing treatment and there is a need to use internal breakers when surfactant-based acids are used in dry gas wells or water injectors. Second, hydrolysis at high temperatures has great impact on surfactant-acid rheological properties. Short time viscosity build-up and effective gel break-down can be achieved if surfactant-acid treatments are carefully designed; otherwise, unexpected viscosity reduction and phase separation may occur, which will affect the outcome of acid treatments.

A solid breaker is used to reduce the viscosity of the gel at pH range of 4-5 for in-situ gelled acids with Zr4 cross-linkers utilize. However, the literature survey confirmed that solid breakers caused a premature reduction in the fluid viscosity resulting in a less than desirable productivity. Therefore, an effective liquid breaker that is based on tetrafluoroboric acid was developed. This study was conducted to evaluate this new breaker system under the following conditions: breaker concentration (0-200 ppm), and acid injection rate (0.5-10 cm3/min). The major findings from the performed viscosity measurements and single coreflood experiments can be summarized as follows: the crosslinking of the polymer occurred at a pH value of 1.8. At a pH of less than 2, doubling the breaker concentration did not affect the viscosity of the acid. However, at a pH of greater than 2, the viscosity of acid was reduced by 30 percent. At a breaker concentration of 0 ppm, the appearance of Zr in the core effluent sample was delayed by 0.25 PV compared to the reaction product, while at 100 ppm, Zr was delayed by 0.75 PV. At 200 ppm breaker, no Zr ions were detected in the effluent samples. Additionally, it was observed that as the breaker concentration increased, more Zr remained inside the core, as ZrF4, which is water-insoluble. Increasing the breaker concentration from 100 to 200 ppm reduced the final normalized pressure drop by 50 percent at injection rate of 2.5 cm3/min. Permeability reduction due to gel was reduced by increasing the acid injection rate.