Building a Fundamental Understanding of Scale-Inhibitor Retention in Carbonate Formations

The development of effective scale-inhibitor (SI) squeeze treatments remains a challenge for carbonate reservoirs because of their substantial chemical reactivity with the SI. This in turn might potentially lead to uncontrolled SI precipitation and induced formation damage. This work takes a systematic approach to understanding the retention mechanisms of SI in carbonate formations with respect to the detailed carbonate-formation mineralogy, type of SI, and reservoir conditions in the absence of oil. Static adsorption/ compatibility experiments, described previously as apparent adsorption tests (Kahrwad 2008), were performed to evaluate the areas of different retention mechanisms [pure adsorption (C) and coupled adsorption/precipitation (C/P)] of different SI species in brine. Experiments were conducted for five SIs at various conditions: initial pH values, mineralogical compositions (calcite, limestone, and dolomite), and temperatures. The SI species used in this study included a phosphonate [di-ethylene tetra-amine penta (DETPMP)], a phosphate ester [polyhydric alcohol phosphate ester (PAPE)], and three polymeric SIs [polyphosphino carboxylic acid (PPCA), P-functionalized copolymer (PFC), and sulfonated polyacrylic acid copolymer (VS-Co)]. All precipitates were studied using environmental scanning electron microscopy/energy dispersive X-ray (ESEM/EDX) and particle-size analysis (PSA). The overall results from these coupled C/P experiments are as follows: • For the polymeric SIs (PPCA, PFC, and VS-Co), the highest retention levels were observed at low pH for all carbonate substrates, because of the increase in divalent cations calcium and magnesium (Ca^2þ and Mg^2þ, respectively) available from rock dissolution for SI–M^2þ ions (divalent cations) precipitation. For DETPMP and PAPE SIs, the retention level was greatest at higher pH values, because the SI functional groups were more dissociated and, hence, available for complexation with M^2þ ions. • The polymeric VS-Co predominantly showed pure adsorption with only a low amount of precipitation (C_app ≈ 1.2 mg/g) in contact with the dolomite substrate. This is because of the presence of sulfonate groups (low pK_a). • For polymeric inhibitors, the retention level (C_app) was highest on calcite (highest relative calcium content), followed by limestone and dolomite. DETPMP and PAPE SIs showed the highest retention levels on dolomite (higher final solution pH and more SI dissociated), followed by limestone and calcite. • For all SI species, higher retention (more precipitation, P) was observed at elevated temperatures. At lower temperatures, an extended region of pure adsorption was observed for all SIs. The information presented in this study will be helpful in SI product selection on the basis of mineralogy and reservoir conditions. As a consequence, longer squeeze lifetimes and improved efficiency of SI deployment in carbonate reservoirs can be achieved. In addition, this study provides valuable data for validating models of the SI/carbonate/Ca/Mg system that can be incorporated into squeeze design simulations.