Amino acid-assisted effect on hydrate-based CO2 storage in porous media with brine.

CO2 storage as hydrates in porous media is a promising method for storing carbon dioxide (CO2). However, the sluggish formation kinetics of hydrates urge the need to focus on the use of additives (promoters) to accelerate hydrate kinetics. This study investigates the effect of amino acid solutions in brine on CO2 hydrate formation and dissociation kinetics in quartz sand particles QS-2 (0.6-0.8 mm) with 38% porosity. The amino acids l-methionine (l-meth), l-isoleucine (l-iso), and l-threonine (l-threo) were studied at 0.2 wt% using an autoclave hydrate reactor at 4 MPa and 274.15 K in the presence and absence of salt (3.3 wt% NaCl) in 100% water saturation. The hydrate dissociation kinetics was studied at a temperature of 277.15 K. These conditions represent the normal seabed temperature range in Malaysia and hence were used for testing CO2 hydrate formation and dissociation kinetics in quartz sand in this study. Further, CO2 hydrate formation and dissociation experiments were conducted with sodium dodecyl sulphate (SDS) and brine systems as standards for comparison. The findings reveal the best kinetics for l-meth exhibiting the highest CO2 hydrate storage capacity. l-meth recorded a gas-to-hydrate conversion ratio of about 93% at 0.2 wt% in quartz sand with brine. Moreover, l-meth exhibited the lowest hydrate dissociation rate compared to l-iso and l-threo systems, thereby enhancing CO2 hydrate stability in quartz sand. Comparatively, l-meth enhanced the storage capacity by 36% and reduced the induction time by more than 50% compared to conventional promoter SDS in quartz sand with brine, suggesting it to be favorable for CO2 storage applications. CO2 hydrate nucleation time was predicted in quartz sand with and without the best-studied amino acid l-meth system with high prediction accuracy and an absolute average deviation of 2.4 hours. The findings of this study substantiate the influence of amino acids in promoting the storage capacity of CO2 in sediments as hydrates.

Research Advances in Machine Learning Techniques in Gas Hydrate Applications.

The complex modeling accuracy of gas hydrate models has been recently improved owing to the existence of data for machine learning tools. In this review, we discuss most of the machine learning tools used in various hydrate-related areas such as phase behavior predictions, hydrate kinetics, CO2 capture, and gas hydrate natural distribution and saturation. The performance comparison between machine learning and conventional gas hydrate models is also discussed in detail. This review shows that machine learning methods have improved hydrate phase property predictions and could be adopted in current and new gas hydrate simulation software for better and more accurate results.

Kinetic and Thermodynamic Influence of NaCl on Methane Hydrate in an Oil-Dominated System.

This experimental study reports the kinetic and thermodynamic inhibition influence of sodium chloride (NaCl) on methane (CH4) hydrate in an oil-dominated system. To thoroughly examine the inhibition effect of NaCl on CH4 hydrate formation, kinetically by the induction time and relative inhibition performance and thermodynamically by the hydrate liquid-vapor equilibrium (HLwVE) curve, enthalpy (ΔHdiss) and suppression temperature are used to measure the NaCl inhibition performance through this experimental study. All kinetic experiments are performed at a concentration of 1 wt % under a pressure and temperature of 8 MPa and 274.15K, respectively, whereby for the thermodynamic study, the concentration was 3 wt % by using the isochoric T-cycle technique at the selected range of pressures and temperatures of 4.0-9.0 MPa and 276.5-286.0K, respectively; both studies were conducted using a high-pressure reactor cell. Results show that kinetically, NaCl offers slightly to no inhibition in both systems with/without oil; however, the presence of drilling oil contributes positively by increasing the induction time; thermodynamically, NaCl contributes significantly in shifting the equilibrium curve to higher pressures and lower temperatures in both systems. In the oil system, the contribution of the THI to the equilibrium curve increases the pressure with a range of 0.04-0.15 MPa and reduces the temperature with a range of 1-3 K, which is due to the NaCl presence in the systems that reduces the activity of water molecules by increasing the ionic strength of the solution. At a high pressure of 9 MPa, the NaCl inhibition performance was greater than that at lower pressures <5.5 MPa because, at the high pressure, NaCl increases the activity of water, which means that more water molecules are available to form hydrate cages around gas molecules.

Robust Carborane-Based Metal-Organic Frameworks for Hexane Separation.

Hexane isomers play a vital role as feedstocks and fuel additives in the petrochemical industry. However, their similar physical and chemical properties lead to significant challenges in the separation process. Traditional thermal separation techniques are energy-intensive and lead to significant carbon footprint penalties. As such, there is a growing demand for the development of less energy-intensive nonthermal separation methods. Adsorption-based separation methods, such as using solid sorbents or membranes, have emerged as promising alternatives to distillation. Here, we report the successful synthesis of two novel metal-organic frameworks (MOFs), NU-2004 and NU-2005, by incorporating a carborane-based three-dimensional (3D) linker and using aluminum and vanadium nodes, respectively. These MOFs exhibit exceptional thermal stability and structural rigidity compared to other MIL-53 analogues, which is further corroborated using synchrotron studies. Furthermore, the inclusion of the quasi-spherical 3D linker in NU-2004 demonstrates significant advancements in the separation of hexane isomers compared to other MIL MOFs containing two-dimensional (2D) and aliphatic 3D linkers.

Pore Aperture Control Toward Size-Exclusion-Based Hydrocarbon Separations.

Metal-organic frameworks (MOFs) have been proposed as a promising material for non-thermal chemical separations owing to their high structural diversity and tunability. Here, we report the synthesis of a zinc-based MOF containing a three-dimensional (3D) linker, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, with high thermal stability towards the separation of hexane isomers. The incorporation of the 3D linker enhances the structural stability and provides well-defined pore apertures/channels with sub-Ångstrom precision. This precision allowed for the separation of similarly sized hexane isomers based on subtle differences in their kinetic diameters. Multi-component liquid phase batch experiments confirmed the separation of hexanes mixture into linear, monobranched, and dibranched isomers. This work represents a significant milestone in the construction of stable Zn-based MOFs and the incorporation of 3D linkers as a potential solution to challenging separations.

Estimation of Thermodynamic Stability of Methane and Carbon Dioxide Hydrates in the Presence of Hydrogen Sulfide.

This work presents the effect of hydrogen sulfide gas on the phase behavior of both methane gas hydrate formation and CO2 gas hydrate formation. For this, the thermodynamic equilibrium conditions for various gas mixtures containing CH4/H2S and CO2/H2S are initially found by simulation using PVTSim software. These simulated results are compared using an experimental approach and the available literature. Then, the thermodynamic equilibrium conditions generated by simulation are used for generating Hydrate Liquid-Vapor-Equilibrium (HLVE) curves to understand the phase behavior of gases. Further, the effect of hydrogen sulfide on the thermodynamic stability of methane and carbon dioxide hydrates was studied. It was clearly observed from the results that an increase in H2S composition in the gas mixture decreases the stability of CH4 and CO2 hydrates.

Inhibitory influence of amino acids on the formation kinetics of methane hydrates in oil-water and oil-brine systems.

This experimental study evaluates the inhibition performance of kinetic hydrates inhibitors (KHIs) of three amino acids, namely: glycine, proline, and alanine. It includes the performance comparison with the conventional inhibitor i.e., polyvinyl pyrrolidine (PVP) on methane (CH4) hydrate in oil systems in two different systems, i.e., deionized and brine water systems. The experiments were conducted in a high-pressure hydrate reactor replicating subsea pipeline conditions, i.e., the temperature of 274 K, pressure 8 MPa, and concentration of 1 wt%, by applying the isochoric cooling technique. The formation kinetics results suggest that all the studied amino acids effectively worked as kinetic inhibitors by potentially delaying CH4 hydrate formations due to their steric hindrance abilities. The interesting phenomenon was observed that the different studied amino acids behave differently in the brine-oil and deionized water-oil systems due to their side chain interaction. In a deionized water-oil system, glycine gives the highest inhibition performance by reducing the hydrate formation risk. On the contrary, in the brine-oil system, proline showed a significant inhibition effect. It should be noted that both glycine and proline were giving almost similar inhibition performance compared to the conventional hydrate inhibitor PVP, however glycine and proline significantly reduced CH4 consumption into hydrate due to their high surface active under CH4 conditions, which strengths the surface tension of the liquid/CH4 interface. Furthermore, according to the findings, it shows that increased side alkyl chain lengths of amino acids increase the efficacy of their kinetic hydration inhibition performance due to better surface adsorption abilities. The amino acids' ability to suppress growth is also linked strongly with hydrophobicity and alkyl side chain length. The findings of this study contribute significantly to current efforts to limit gas hydrate formation in offshore pipelines, particularly in oil-dominant pipelines.

Methane and Carbon Dioxide Hydrate Formation in the Presence of Metal-Based Fluid.

Hydrate-based technology has yet to find its way to commercial applications due to several issues, including formation conditions and slow kinetics. Several solid particles were introduced to speed up hydrate formation. However, these solid compounds have given contradictory results. This study investigated the effect of high thermal conductive metallic nanofluids of silver (Ag) and copper (Cu) on CH4 and CO2 hydrates. The solid particles were suspended in a 0.03 wt% SDS aqueous solution, and the results were compared with the 0.03 wt% SDS and deionized water samples. A stirred tank batch reactor was used to conduct the thermodynamic and kinetic experiments. The thermodynamic study revealed that 0.1 wt% of solid particles do not shift the equilibrium curve significantly. The kinetic evaluation, including induction time, the initial rate of gas consumption, half-completion time, t50 and semi-completion time, t95, gas uptake, and storage capacity, have been studied. The results show that the Ag and Cu promote CH4 hydrates while they inhibit or do not significantly influence the CO2 hydrates formation. A predictive correlation was introduced to get the apparent rate constant of hydrate formation in the presence of metal-based fluid at the concentrations range of 0.005-0.1 wt%.

Correction to "Gas Hydrate in Oil-Dominant Systems: A Review".

[This corrects the article DOI: 10.1021/acsomega.2c02278.].

Experimental investigation and modelling of synergistic thermodynamic inhibition of Diethylene Glycol and glycine mixture on CO2 gas hydrates.

In this experimental and modelling study, Diethylene glycol (DEG) and Glycine (Gly) mixtures are introduced to hinder carbon dioxide hydrate formation by pushing the phase boundaries on the lower temperature side. The mixture of DEG and Gly with the ratio of 1:1 is experimented at 15, 10, and 5 wt% concentrations and the pressure vary from 2.5 to 4.0 MPa. The T-cycle method is employed to assess the effect of the studied blends on the CO2 hydrate by evaluating the hydrate dissociation temperature. Varied compositions of pure DEG and Gly as well as their mixtures are used to compute the synergistic effect. The studied system's thermodynamic hydrate inhibition (THI) influence is a concentration-driven phenomenon. Higher concentration can shift the hydrate liquid vapor equilibrium (HLVE) curve to lower temperatures and high-pressure regions. The outcomes depict that mixture of DEG and Gly at 15 wt%. Shows comparatively better results than the mixtures at 5 and 10 wt%, respectively. The obtained 10 wt% mixture results have also been compared with the conventional hydrate inhibitors and other THIs systems and provide a significant hydrate average suppression (ΔT) of 2.4 K. Furthermore, the freezing point-based Dickens and Quint Hunt model was also applied to predict the HLVE data of CO2 hydrates and satisfactory agreement found with maximum mean absolute error (MAE) of 0.498 K. A better inhibitory performance was seen when diethylene glycol and glycine were combined, demonstrating the potential of amino acids as synergistic inhibitors in the exploitation of hydrates, transportation of oil and gas, and flow assurance.

Gas Hydrate in Oil-Dominant Systems: A Review.

Gas hydrate risks minimization in deepsea hydrocarbon flowlines, especially in high water to oil ratios, and is critical for the oil and gas flow assurance industry. Although there are several reviews on gas hydrate mitigation in gas-dominated systems, limited reviews have been dedicated to the understanding and mechanism of hydrate formation and mitigation in oil-dominated systems. Hence, this review article discusses and summarizes the prior studies on the hydrate formation behavior and mitigation in oil-dominated multiphase systems. The factors (such as oil volume or water cut, bubble point, and hydrate formers) that affect hydrate formation in oil systems are also discussed in detail. Furthermore, insight into the hydrate mitigation and mechanism in oil systems is also presented in this review. Also, a detailed table on the various studied hydrate tests in oil systems, including the experimental methods, inhibitor type, conventions, and testing conditions, is provided in this work. The findings presented in this work are relevant for developing the best solution to manage hydrate formation in oil-dominated systems for the oil and gas industry.

Effect of ammonium hydroxide-based ionic liquids' freezing point and hydrogen bonding on suppression temperature of different gas hydrates.

The study presents the effect of freezing point depression and hydrogen bonding energy interaction on four ammonium hydroxide-based ionic liquids (AHILs) of gas hydrate systems. The AHILs investigated are tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. The considered hydrate system includes methane (CH4), carbon dioxide (CO2), and three binary mixed gas hydrates (70-30 CO2 + CH4, 50-50 CO2 + CH4, 30-70 CO2 + CH4), which are often encountered in the flow assurance pipelines. The experimental temperature range is between 274.0 and 285.0 K, corresponding to pipeline pressures for different gas systems. The thermodynamic influence, i.e., average suppression temperature (ΔT) of the studied system, was reported for different mass concentrations (1, 5, and 10 wt%) and correlated with the freezing point depression and hydrogen bonding energy interaction of AHILs. The study also covers the structural impact of AHILs (in the form of alkyl chain variation) on the thermodynamic hydrate inhibition (THI) behaviour via freezing point and hydrogen bonding energy interactions. Findings revealed that the increased alkyl chain length of AHILs reduced the ΔT due to a decrease in hydrogen bonding ability. The highest THI inhibition (ΔT = 2.27 K) is attained from the lower alkyl chain AHIL, i.e., TMAOH (10 wt%) for the CO2 hydrate system. The freezing point depression of AHILs is a concentration-dependent phenomenon. Increased concentration of the AHILs in the system yielded lower freezing point temperature, positively influencing hydrate mitigation. Although the study provided the initial insight between the freezing point tendency and hydrogen bonding energies of AHILs on thermodynamic inhibition (ΔT). Based on the freezing point depression and hydrogen bonding energy interaction, a more generalized correlation should be developed to predict any potential ionic liquids regarded as promising hydrate inhibitors.

Correction to "Suitable Binary and Ternary Thermodynamic Conditions for Hydrate Mixtures of CH4, CO2, and C3H8 for Gas Hydrate-Based Applications".

[This corrects the article DOI: 10.1021/acsomega.1c06186.].

Suitable Binary and Ternary Thermodynamic Conditions for Hydrate Mixtures of CH4, CO2, and C3H8 for Gas Hydrate-Based Applications.

The selection of suitable hydrate formers and their respective gas composition for high hydrate formation, driving force is critical to achieve high water recovery and metal removal efficiency in the hydrate-based desalination process. This study presents a feasibility analysis on the possible driving force and subcooling temperatures for the binary and ternary mixtures of methane, carbon dioxide, and propane for hydrates-based desalination process. The driving force and subcooling for the gas systems was evaluated by predicting their hydrate formation phase boundary conditions in 2 wt % NaCl systems at pressure ranges from 2.0-4.0 MPa and temperatures of 1-4 °C using modified Peng-Robinson equation of state in the PVTSim software package. The results suggest that the driving force of CH4 + C3H8 and CO2 + C3H8 binary systems are similar to their ternary systems. Thus, the use of binary systems is preferable and simpler than the ternary systems. For binary gas composition, CO2 + C3H8 (70:30) exhibited a higher subcooling temperature of 8.07 °C and driving force of 1.49 MPa in the presence of 2 wt % aqueous solution. In the case of the ternary system, CH4-C3H8-CO2 gas composition of 10:80:10 provided a good subcooling temperature of 12.86 °C and driving force of 1.657 MPa for hydrate formation. The results favor CO2-C3H8 as a preferred hydrate former for hydrate-based desalination. This is attributed to the formation of sII structure and it constitutes 136 water molecules which signifies a huge potential of producing more quantities of treated water.

Visible-Light-Driven Carbon-Doped TiO2-Based Nanocatalysts for Enhanced Activity toward Microbes and Removal of Dye.

Solar-driven photocatalytic approach is an attractive, clean, and effective way for decontamination of water. In this work, visible-light-activated TiO2 nanoflakes (TNFs) and carbon-doped TiO2 nanoflakes (C-TNFs) were synthesized via a facile hydrothermal route using different carbon sources. The as-synthesized nanostructures were successfully characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM), critically disclosing the anatase nature containing titanium-oxygen having flake/platelet-like morphology with ∼32 nm in size, respectively. The photocatalytic activity was characterized via the degradation of methylene blue (MB) and bacterial inactivation of Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive). The experimental results showed that C-TNFs significantly enhanced photocatalytic activity compared to bare TNFs. It was found that TNF nanocatalysts exhibited superior photocatalytic activity against photodegradation of MB (92.7%) and antibacterial activity (85.6%) under sunlight irradiation. In addition, reduced graphene oxide (RGO)-TNFs have a good recycling ability and are expected to be a promising candidate for photocatalytic applications under sunlight. Consequentially, the higher activity of RGO-TNF nanocatalysts under sunlight irradiation for organic degradation and bacterial inactivation implies that hydrothermal synthesis allows for the preparation of efficient and low-cost carbon-doped photocatalysts for the photodegradation of a wide range of environmental pollutants.

Investigation on Thermodynamic Equilibrium Conditions of Methane Hydrates in Multiphase Gas-Dominant Pipelines.

The estimation of thermodynamic equilibrium conditions of methane hydrates in the presence of crude oil based on experiments is shown in this research work. This pipeline system replicated the gas-dominant multiphase transmission pipelines at deep-sea regions. An experimental study is done by the usage of a Raman gas hydrate reactor. The pressure was maintained in the range of 3-8 MPa for the experimental study. The water cut is kept constant throughout the system as 30%. Initially, the experimental setup is calibrated by using carbon dioxide gas. Then, methane hydrates are formed with and without crude oil. The methane hydrates that are created without the presence of crude oil are validated with simulation that is performed using CSMGEM, PVTSIM software, and literature data. Then, the thermodynamic conditions are found for the methane hydrate formation in the presence of crude oil with an addition of a 15% oil cut to the system. From these results, the phase behavior of a multiphase system is evaluated. The formation of methane hydrates in the system was found to be affected by the presence of an additional oil phase that exhibited an inhibition behavior. This research validates all the multiphase systems that contain similar hydrocarbon and gas compositions.

Experimental and modeling studies on enhancing the thermodynamic hydrate inhibition performance of monoethylene glycol via synergistic green material.

This paper presents an experimental and modeling studies on the thermodynamic inhibition effects of the mixture of monoethlyene glycol (MEG) and glycine (Gly) on the carbon dioxide hydrate phase boundary condition. The monoethlyene glycol and glycine (1:1) mixture inhibition effects were investigated at concentrations of 5, 10, and 15 wt.% and pressure ranges from 2.0-4.0 MPa. The effects of the proposed mixture on the carbon dioxide hydrate phase boundary were evaluated by measuring the dissociation temperature of carbon dioxide hydrate using a T-cycle method. The synergistic effect was evaluated based on comparison with pure MEG and Gly data. The results show that 15 wt.% of MEG and Gly mixture displays the highest inhibition effect compared to the 5 and 10 wt.% mixtures, respectively. However, the synergistic effect is higher at 10 wt.%. Dickens' model was also adopted to predict the phase equilibrium data of CO2 hydrates in the presence of the mixture. The modified model successfully predicted the data within a maximum error of ± 0.52 K.

Kinetic Behavior of Quaternary Ammonium Hydroxides in Mixed Methane and Carbon Dioxide Hydrates.

This study evaluates the kinetic hydrate inhibition (KHI) performance of four quaternary ammonium hydroxides (QAH) on mixed CH4 + CO2 hydrate systems. The studied QAHs are; tetraethylammonium hydroxide (TEAOH), tetrabutylammonium hydroxide (TBAOH), tetramethylammonium hydroxide (TMAOH), and tetrapropylammonium hydroxide (TPrAOH). The test was performed in a high-pressure hydrate reactor at temperatures of 274.0 K and 277.0 K, and a concentration of 1 wt.% using the isochoric cooling method. The kinetics results suggest that all the QAHs potentially delayed mixed CH4 + CO2 hydrates formation due to their steric hindrance abilities. The presence of QAHs reduced hydrate formation risk than the conventional hydrate inhibitor, PVP, at higher subcooling conditions. The findings indicate that increasing QAHs alkyl chain lengths increase their kinetic hydrate inhibition efficacies due to better surface adsorption abilities. QAHs with longer chain lengths have lesser amounts of solute particles to prevent hydrate formation. The outcomes of this study contribute significantly to current efforts to control gas hydrate formation in offshore petroleum pipelines.

Phase behavior study on gas hydrates formation in gas dominant multiphase pipelines with crude oil and high CO2 mixed gas.

This research is focused on understanding the phase behavior of gas hydrate formation in the gas dominant multiphase pipelines containing mixed gas with high CO2, crude oil, and deionized water. The experimental conditions are in the pressure range of 3-7 MPa with water cut as 20% of the volume. Initially, the effect of high CO2 content in natural gas on the phase boundary conditions of hydrates is studied through simulation (CSMGEM software) and experiments. Later, an additional phase of crude oil was introduced, with 15% of the volume to study the multiphase system. From the experimental analysis, thermodynamic equilibrium conditions were found, and the hydrate-liquid-vapor-equilibrium (HLVE) curves were drawn. The phase behavior is comprehended by comparing the HLVE curves of pure and multiphase systems. It is found that the high CO2 content tends to promote the gas hydrate formation. Based on the results, temperature variance and enthalpy of formation were calculated for the multiphase system. With a difference of 1.32 average temperature variance, the multiphase system exhibits inhibition. A basic statistical regression model was made to predict the gas hydrate formation in multiphase transmission pipelines. This work helps in understanding the effect of a new phase on gas hydrate formation.

Rheology Impact of Various Hydrophilic-Hydrophobic Balance (HLB) Index Non-Ionic Surfactants on Cyclopentane Hydrates.

In this study, series of non-ionic surfactants from Span and Tween are evaluated for their ability to affect the viscosity profile of cyclopentane hydrate slurry. The surfactants; Span 20, Span 40, Span 80, Tween 20, Tween 40 and Tween 80 were selected and tested to provide different hydrophilic-hydrophobic balance values and allow evaluation their solubility impact on hydrate formation and growth time. The study was performed by using a HAAKE ViscotesterTM 500 at 2 °C and a surfactant concentration ranging from 0.1 wt%-1 wt%. The solubility characteristic of the non-ionic surfactants changed the hydrate slurry in different ways with surfactants type and varying concentration. The rheological measurement suggested that oil-soluble Span surfactants was generally inhibitive to hydrate formation by extending the hydrate induction time. However, an opposite effect was observed for the Tween surfactants. On the other hand, both Span and Tween demonstrated promoting effect to accelerate hydrate growth time of cyclopentane hydrate formation. The average hydrate crystallization growth time of the blank sample was reduced by 86% and 68% by Tween and Span surfactants at 1 wt%, respectively. The findings in this study are useful to understand the rheological behavior of surfactants in hydrate slurry.