Quantification of the effect of gas–water–equilibria on carbonate precipitation

The expanding geothermal energy sector still faces performance issues due to scalings in pipes and surface level installations, which require elevated operation pressure levels and costly maintenance. For facilities in the North Alpine Foreland Basin, the precipitation of \({\hbox {CaCO}}_{3}\) is the main problem which is a consequence of the disruption of the lime-carbonic acid equilibrium during production. The formation of gas bubbles plays a key role in the scaling process. This work presents experiments in a bubble column to quantify the effects of gas stripping on carbonate precipitation and an extension of PhreeqC to include kinetic exchange between a gas phase and water for the simulation of the experimental results. With the same hybrid model not only precipitation of \({\hbox {CaCO}}_{3}\) but also the dissolution of scalings by the injection of \({\hbox {CO}}_{2}\) could be quantified. The bubble column was filled with tap water and brine. By varying the ionic strength of the solution, a wider range of geothermal waters was covered. Air and \({\hbox {CO}}_{2}\) were introduced at the bottom. The precipitates built on the column wall were analyzed with Raman spectroscopy: injecting air into tap water at low ionic strength led to the formation of aragonite with 59.8% of the precipitates remaining at the column wall and the rest as particles in dispersion. At moderate ionic strength the dominant polymorph was calcite and 81.5% of the crystals were attached to the wall. At high ionic strength precipitation was inhibited. The presence of crystallization nuclei reduced the time for precipitation, but not the amount of scalings formed. Injecting \({\hbox {CO}}_{2}\) into the solution completely removed the scalings from the column wall. The model and its experimental backup lay the foundation for a process-based prediction of the scales (not only) in geothermal systems.