Effect of precipitation procedure and detection technique on particle size distribution of CaCO3

The deposition of inorganic salts (“scales”) such as calcium carbonate is an important flow assurance problem during crude oil production. The knowledge of the features of the precipitated solids, mainly the particle size and morphology, is crucial to understand the nature of the solids and to avoid or reduce the effect of their deposition. For instance, the use of additives is one of the most usual procedures to mitigate this problem. Additives interact with scale-forming substances either by increasing the induction time, or by inhibiting crystal growth, changing the morphology of solids.In this work, CaCO3 was precipitated by two different experimental methods: by mixing sodium carbonate and calcium chloride at 25 °C (method 1), and by changing the pH (method 2). Precipitated solids were analyzed by means of the following techniques: laser diffraction (LD), focused-beam reflectance measurement (FBRM), scanning electron microscopy (SEM), and X-ray diffraction (XRD), in order to select a method for the determination of particle size of solids similar to scales, in order to study these deposits at the beginning of their formation and to evaluate the effect of additives in the scales particle size. Results were compared to those of scale deposits extracted from crude oil pipelines.SEM and XRD characterization showed that both the precipitation methods lead to calcium carbonate as a mixture of calcite, aragonite and vaterite, with rhombohedral morphology for method 1 and spherical for method 2. The effects of temperature, kinetics and Mg2+ presence in the morphology of CaCO3 were evaluated. Thus, the solids obtained by static bottle test and real scales are mainly formed by long needle-shaped aragonite. The comparison of the several particle size characterization methods determinates that an LD is a fast and sensitive technique for spherical and non-spherical solids, and it is a convenient technique for the analysis of scales extracted from oil pipelines.