Tzachristas Andreas, Kanellopoulou Dimitra, Parthenios John, Koutsoukos Petros G, Paraskeva Christakis, Sygouni Varvara
Department of Chemical Engineering, University of Patras, Karatheodori 1, 26504 Patras, Greece.
Institute of Chemical Engineering, Foundation for Research and Technology-Hellas, Stadiou str., Platani, 26504 Patras, Greece.
Langmuir. 2025 Jun 3;41(21):13506-13515. doi: 10.1021/acs.langmuir.5c01363. Epub 2025 May 16.
The control of calcium carbonate formation is of high importance for a wide range of applications in the pharmaceutical industry and membrane processes as well as in the oil and gas industry. Herein, for the first time, the effect of monoethylene glycol (MEG) on the formation of calcium carbonate (CaCO) crystals from supersaturated solutions flowing through microchannels (volume 0.36 mL) of varying wettability was investigated. The use of microdevices enabled the observation of the scaling phenomenon in the early stages. Solutions supersaturated with respect to calcite, containing MEG (10, 20, and 30% v/v), were injected into the microchannel under a constant total flow rate and under laminar flow conditions (Re = 0.052). The growth of calcium carbonate crystals was monitored by video recording. The effect of the wettability on crystal formation was tested using glass and silane-coated microchips. The microchannel walls were wet and neutral-wet by the supersaturated solutions with a low MEG concentration. In the presence of a high MEG concentration in the supersaturated solutions, the walls of both types of microchips were neutral-wet. The results showed that the addition of MEG at a concentration of 10% v/v in the supersaturated solutions decreased the time of observation of the first crystal, favored secondary nucleation, and in general decreased the crystal growth rates. Raman spectroscopy identified the formation of aragonite in most cases, while as SR values increased, the formation of aragonite aggregates was favored. Further increases of the MEG concentration in the supersaturated solutions to 20% v/v, at low supersaturation ratio (SR) values, favored the formation of amorphous calcium carbonate (ACC) while at higher SR values aragonite crystals and aragonite aggregates formed. Further increases in the MEG concentration in the supersaturated solutions up to 30% v/v completely inhibited the nucleation and crystal growth of calcium carbonate.
碳酸钙形成的控制对于制药行业、膜过程以及石油和天然气行业中的广泛应用至关重要。在此,首次研究了单乙二醇(MEG)对碳酸钙(CaCO)晶体从流经不同润湿性微通道(体积0.36 mL)的过饱和溶液中形成的影响。微器件的使用使得能够观察到早期的结垢现象。将相对于方解石过饱和且含有MEG(10%、20%和30% v/v)的溶液在恒定总流速和层流条件(Re = 0.052)下注入微通道。通过视频记录监测碳酸钙晶体的生长。使用玻璃和硅烷涂层微芯片测试润湿性对晶体形成的影响。低MEG浓度的过饱和溶液使微通道壁呈湿润和中性湿润状态。在过饱和溶液中存在高MEG浓度时,两种类型微芯片的壁均呈中性湿润状态。结果表明,在过饱和溶液中添加10% v/v浓度的MEG可缩短首次观察到晶体的时间,有利于二次成核,总体上降低晶体生长速率。拉曼光谱在大多数情况下鉴定出文石的形成,而随着SR值增加,有利于文石聚集体的形成。当过饱和溶液中MEG浓度进一步增加到20% v/v时,在低过饱和度比(SR)值下有利于无定形碳酸钙(ACC)的形成,而在较高SR值下形成文石晶体和文石聚集体。当过饱和溶液中MEG浓度进一步增加至30% v/v时,完全抑制了碳酸钙的成核和晶体生长。