Scale-inhibitor (SI) squeeze treatments are applied extensively for controlling scale formation during oil and gas production. The current research involves phosphonate/metal precipitate studies in the context of precipitation-squeeze treatments. The main focus here is on the precipitation and solubility behavior of the SI_calcium (Ca)_magnesium (Mg) complexes of HEDP (a diphosphonate), DETPMP (a pentaphosphonate), and OMTHP (a hexaphosphonate); these mixed phosphonate/divalent precipitates are denoted as SI_Can1_Mgn2, where n1 and n2 are the stoichiometric ratios of Ca and Mg to SI, respectively.
Precipitation experiments with SI_Can1_Mgn2 species were carried out over a temperature range of 20 to 95°C, while varying the Mg/Ca molar ratio over a wide range from all Ca to all Mg. These precipitates were formed in MgCl2·6H2O/CaCl2·6H2O brine solutions with appropriate molar ratios of metals, then separated from the supernatant by filtration. Subsequently, the solubility of the collected precipitate was found in a solution of the same Mg/Ca molar composition from which it was prepared. In this type of experiment, the solubility of the SI_Can1_Mgn2 precipitate without any respeciation is determined. In addition, another type of solubility experiment was carried out for a precipitate formed in a brine with one fixed Mg/Ca ratio; this was subsequently placed into a solution with different Mg/Ca compositions (from all Ca to all Mg). In these experiments, respeciation of the precipitate may occur.
We have been able to establish the solubility (Cs) of the precipitates of three SIs (HEDP, OMTHP, and DETPMP) as a function of both temperature and Mg/Ca molar ratio. It has been shown that the solubility of precipitate is in equilibrium with Mg and Ca concentrations in solution, and any change of these parameters leads to solubility variation. All phosphonate/metal precipitates become less soluble with increasing temperature and much more soluble with an increasing proportion of Mg. We have found that any change in Mg/Ca ratio of brine does lead to a redistribution of Ca, Mg, and SI concentrations in a given precipitate and bulk solution, and, hence, leads to some variation in the precipitate solubility.
Additionally, the inhibition efficiency (IE) of precipitated and then redissolved HEDP, OMTHP, and DETPMP SIs was tested and compared with the IE of industrial stock products. We show that, unlike polymeric SI precipitates, the inhibition activity of phosphonate SIs does not depend significantly on the precipitation process, and the IE of precipitated and redissolved SI_Ca and SI_Ca_Mg complexes is very close to that of the industrial stock solutions. These results can be used directly for modeling phosphonate precipitation-squeeze treatments, and the significance of these results for field applications is explained.