The Effect of pH and Mineralogy on the Retention of Polymeric Scale Inhibitors on Carbonate Rocks for Precipitation Squeeze Treatments

The bulk "apparent adsorption" behavior (G_app, vs. C_f) of 2 polymeric scale inhibitors (SI), PPCA and PFC, onto carbonate mineral substrates has been studied for initial solution pH values of pH 2, 4 and 6. The 2 carbonate minerals used, calcite and dolomite, are much more chemically reactive than sandstone minerals (e.g. quartz, feldspars, clays etc.) which have already been studied extensively. In nearly all cases, precipitates formed at higher SI concentrations were due to the formation of sparingly soluble SI/Ca complexes. A systematic study has been carried out on the SI/Ca precipitates formed, by applying both ESEM/EDX and particle size analysis (PSA), and this identifies the morphology and the approximate composition of the precipitates. For PPCA, at all initial solution pH values, regions of pure adsorption (G) ([PPCA] <100ppm) and coupled adsorption/precipitation (G/?) are clearly observed for both calcite and dolomite. PFC at pH = 4 and 6 also showed very similar behavior with a region of pure adsorption (G) for [PFC] < 500ppm and a region of coupled adsorption/precipitation (G/?) above this level. However, the PFC/calcite case at pH 2 showed only pure adsorption, while the PFC/dolomite case at pH 2 again showed coupled adsorption/precipitation at higher PFC concentrations. For both SIs on both carbonate substrates, precipitation is the more dominant mechanism for SI retention than adsorption above a minimum concentration of ∼100-500 ppm SI. The actual amount of precipitate formed varies from case to case, depending on the specific SI, substrate (calcite/dolomite) and initial pH (pH 2, 4 and 6). Although the qualitative behavior of both PPCA and PFC was similar on both carbonate substrates, the apparent adsorption of PPCA was higher on calcite than on dolomite; PFC apparent adsorption was higher on dolomite than on calcite. It is discussed in the paper how these observations are related to the reactivity of the different carbonate minerals, the resulting final pH (which affects the dissociation of the SI), Ca-SI binding and the solubility of the resulting complex.