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Surface Precipitation And Growth Kinetics Of Calcium Carbonate (Caco3) Scale Using A Novel Capillary Flow Rig

Picture for Surface Precipitation And Growth Kinetics Of Calcium Carbonate (Caco3) Scale Using A Novel Capillary Flow Rig
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Product Number: 51321-16560-SG
Author: Kabir Raheem/ Thibaut Charpentier/ Olujide Sanni/ Anne Neville
Publication Date: 2021
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The oil and gas industry is plagued with various flow assurance challenges including the formation of inorganic scale on component surfaces. Much research into scaling and inhibition is now being directed towards surface deposition as fouling on surfaces often causes operational problems and the rates cannot be predicted by consideration of bulk precipitation processes. However, achieving a mechanistic understanding of surface kinetics requires laboratory techniques that offer the ability to control thermodynamic parameters. A novel once-through capillary flow rig design based on the conventional tube blocking methodology was used to evaluate the surface formation of CaCO3 under dynamic flowing conditions; an important attribute of this set-up is that saturation ratio (SR) remains constant in the capillary cell due to the short residence time of the flowing brine, and conditions can be such that there is no bulk (pre-precipitated) crystals in the solution when it flows through the cell. This allows the decoupling of bulk and surface scaling, enabling the reliable assessment of the kinetics of scale deposits present in the capillaries and provides an improved mechanistic understanding of mineral scaling on surfaces. CaCO3 surface scaling kinetics was investigated by evaluating the induction times and gravimetric measurements of mass gain in the capillary cell. Scale precipitation tests were carried out on as-received (plain) and functionalized stainless steel substrates at three saturation ratios and flow rates ranging from 10-30 ml/min. Analyses of the induction times and deposition of scale show the significant influence of flow velocity and surface wettability on heterogeneous crystallization processes, and that scale growth on surfaces is not necessarily due to the deposition of bulk precipitated crystals.

Keywords: CaCO3, surface deposition, bulk precipitation, kinetics, capillary cell, dynamic tube, wettability.

The oil and gas industry is plagued with various flow assurance challenges including the formation of inorganic scale on component surfaces. Much research into scaling and inhibition is now being directed towards surface deposition as fouling on surfaces often causes operational problems and the rates cannot be predicted by consideration of bulk precipitation processes. However, achieving a mechanistic understanding of surface kinetics requires laboratory techniques that offer the ability to control thermodynamic parameters. A novel once-through capillary flow rig design based on the conventional tube blocking methodology was used to evaluate the surface formation of CaCO3 under dynamic flowing conditions; an important attribute of this set-up is that saturation ratio (SR) remains constant in the capillary cell due to the short residence time of the flowing brine, and conditions can be such that there is no bulk (pre-precipitated) crystals in the solution when it flows through the cell. This allows the decoupling of bulk and surface scaling, enabling the reliable assessment of the kinetics of scale deposits present in the capillaries and provides an improved mechanistic understanding of mineral scaling on surfaces. CaCO3 surface scaling kinetics was investigated by evaluating the induction times and gravimetric measurements of mass gain in the capillary cell. Scale precipitation tests were carried out on as-received (plain) and functionalized stainless steel substrates at three saturation ratios and flow rates ranging from 10-30 ml/min. Analyses of the induction times and deposition of scale show the significant influence of flow velocity and surface wettability on heterogeneous crystallization processes, and that scale growth on surfaces is not necessarily due to the deposition of bulk precipitated crystals.

Keywords: CaCO3, surface deposition, bulk precipitation, kinetics, capillary cell, dynamic tube, wettability.

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New Understanding on Calcium Carbonate Scaling Kinetics

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Calcium carbonate (CaCO3) is the predominate type of mineral scale formed in many industrial water processes including oil and gas production. Comprehensive and accurate knowledge on the CaCO3 scaling risk is critical for the effective scale management. Currently scale risk assessment is largely depends on thermodynamic simulation which predicts the saturation state under given conditions there are very limited experimental or field data on scaling kinetics. Previous works on temperature effect were investigated on nucleation and precipitation in bulk solutions which didn’t involve the CaCO3 adhesion and accumulation on existing surface. The pressure effect is considered in scaling tendency calculation but its potential impact on scaling kinetics is usually neglected.This paper presents the laboratory results of CaCO3 scaling kinetics at various temperatures (80-150°C) and pressures (500-5000 psia). Tests were conducted with a dynamic tube blocking apparatus which measures CaCO3 scale buildup by monitoring hydrostatic pressure differential (DP) across a capillary tubing and the time for scale formation was determined. Test waters were maintained at similar CaCO3 supersaturation state at different temperatures and pressures by adjusting bicarbonate concentration. Results show that under the test conditions scaling rate was accelerated by both temperature and pressure. CaCO3 scaling time was shortened approximately 2 times when pressure was increased from 500 psi to 5000 psi at the same temperature and similar supersaturation state. For examples scaling timeis decreased from ~65minutes to ~40minutes at 80°C and from ~40 minutes to < 20 minutes at 125°C with pressure changed from 500 psi to 5000 psi..This study provides new understanding on the mineral scaling kinetics by identifying the pressure dependence of CaCO3 scale formation process. Experimental results show that pressure other than its impact on solubility has additional kinetic effect on CaCO3 scaling rate. This kinetic effect should be included in the scaling risk assessment especially for the high pressure systems.
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