Evaluation of the synergic effect of amino acids for CO2 hydrate formation and dissociation

Abstract

Gas hydrate formation is a very challenging problem in the oil and gas industry. The chemical inhibition method is the best practicable hydrate mitigation method by injecting hydrate inhibitors such as Thermodynamic Hydrate Inhibitors (THIs) and Kinetic Hydrate Inhibitors (KHIs) into the pipeline. However, the hydrate inhibitors' biodegradability and limited data on dual functional inhibitor mixtures raise concerns in this study. This study aims to investigate and compare thermodynamic and kinetic inhibition on CO2 hydrate by using biodegradable amino acid inhibitor mixtures of Glycine and Alanine. In this study, the inhibitor mixtures were prepared by mixing Glycine and Alanine in 3 different mixture ratios, followed by the Thermodynamic and Kinetic inhibition tests. Thermodynamic Inhibition Test was conducted by using 10 wt% of inhibitor mixtures in a CO2-water system under pressure of 4.0, 3.5, 3.0 and 2.5 MPa, while Kinetic Inhibition Test was carried out by using 1 wt% of the sample in the CO2-water system at a constant pressure of 4.0 MPa and temperatures at 274.15K. The analysis methods for the Thermodynamic Inhibition Test were Hydrate Liquid-Vapor Equilibrium (HLVE) Curve, Average Depression Temperature and Molar Dissociation Enthalpy, while the Induction Time method, the number of CO2 moles consumed, the formation rate of CO2 gas hydrate and RIP were used in the Kinetic Inhibition Test. In this study, all inhibitor mixtures exhibit dual functional inhibition on the CO2 hydrate. For THI, 50% Gly: 50% Ala shows the best thermodynamic inhibition strength with an average depression temperature of 2.42 K. All the inhibitor mixtures for THI have the dissociation enthalpies within the CO2 hydrate enthalpy range, which show that the inhibition is due to the influence on the water molecules’ interaction only. For KHI, 75% Gly: 25% Ala shows the highest kinetic inhibition strength on CO2 formation with the longest induction time of 115.2 min and the highest RIP of 0.40. In the KHI experiment, there is a drop in the CO2 uptake capacity with the presence of inhibitors used, where the highest difference of CO2 moles consumed is 0.0057 mol. A synergistic effect of inhibitor mixtures was observed in this study on 50% Gly: 50% Ala for THI and 75% Gly: 25% Ala for KHI. However, the “degradation” effect was also exhibited on 75% Gly: 25% Ala and 25% Gly: 75% Ala for THI and 50% Gly: 50% Ala and 25% Gly: 75% Ala for KHI, where the performance of the inhibitor mixtures is poorer than the concentrated amino acids. The “degradation” effect of the inhibitor mixtures at certain ratios was not covered in this study and it requires a further understanding of the chemistry behind the inhibition mechanism.