Experimental and computational investigation of methane hydrate inhibition in the presence of amino acids and ionic liquids

Lee, Dongyoung; Go, Woojin; Seo, Yongwon

doi:10.1016/j.energy.2019.06.025

Cited by 53 publications

(17 citation statements)

References 55 publications

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“…Amino acids tend to behave as zwitterions, which results in a strong electrostatic interaction between the electric charges on the amino acids and the water molecules, which disrupts the structure of the water cages of the hydrates. However, some amino acids, such as glycine, similar to histidine, were shown not to affect the structure of CH 4 hydrate when a powder X-ray diffraction experiment was performed [59]. Different supercooling requirements for different concentrations of a particular chemical indicate different operating requirements to initiate hydrate formation.…”

Section: Constant Ramping Experimentsmentioning

confidence: 99%

Chemically Influenced Self-Preservation Kinetics of CH4 Hydrates below the Sub-Zero Temperature

2021

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The self-preservation property of CH4 hydrates is beneficial for the transportation and storage of natural gas in the form of gas hydrates. Few studies have been conducted on the effects of chemicals (kinetic and thermodynamic promoters) on the self-preservation properties of CH4 hydrates, and most of the available literature is limited to pure water. The novelty of this work is that we have studied and compared the kinetics of CH4 hydrate formation in the presence of amino acids (hydrophobic and hydrophilic) when the temperature dropped below 0 °C. Furthermore, we also investigated the self-preservation of CH4 hydrate in the presence of amino acids. The main results are: (1) At T < 0 ℃, the formation kinetics and the total gas uptake improved in the presence of histidine (hydrophilic) at concentrations greater than 3000 ppm, but no significant change was observed for methionine (hydrophobic), confirming the improvement in the formation kinetics (for hydrophilic amino acids) due to increased subcooling; (2) At T = −2 °C, the presence of amino acids improved the metastability of CH4 hydrate. Increasing the concentration from 3000 to 20,000 ppm enhanced the metastability of CH4 hydrate; (3) Metastability was stronger in the presence of methionine compared to histidine; (4) This study provides experimental evidence for the use of amino acids as CH4 hydrate stabilizers for the storage and transportation of natural gas due to faster formation kinetics, no foam during dissociation, and stronger self-preservation.

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Section: Constant Ramping Experimentsmentioning

confidence: 99%

Chemically Influenced Self-Preservation Kinetics of CH4 Hydrates below the Sub-Zero Temperature

2021

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“…Adsorption inhibition shows that inhibitor molecules are adsorbed on the hydrate crystals, whereas perturbation inhibition works by disturbing the water molecules' structure. In the past decade, ionic liquids (ILs), amino acids (AACs) and quaternary ammonium salts (QAS) [37] have been introduced as green hydrate inhibitors, as well as dual function inhibitors, because they are environmentally friendly and have shown good inhibitory performance as both THIs and KHIs [38][39][40][41][42][43][44][45]. ILs are salts that are generally composed of heterocyclic cations and inorganic anions [38].…”

Section: Thermodynamic Hydrate Inhibitors (This) and Low Dosage Hydramentioning

confidence: 99%

“…In the past decade, ionic liquids (ILs), amino acids (AACs) and quaternary ammonium salts (QAS) [37] have been introduced as green hydrate inhibitors, as well as dual function inhibitors, because they are environmentally friendly and have shown good inhibitory performance as both THIs and KHIs [38][39][40][41][42][43][44][45]. ILs are salts that are generally composed of heterocyclic cations and inorganic anions [38]. ILs have been developed as both green chemicals and designer solvents since their structure and physical properties can be fine-tuned for diverse and specific applications [10,46,47].…”

Section: Thermodynamic Hydrate Inhibitors (This) and Low Dosage Hydramentioning

confidence: 99%

“…Recently, Fatemeh et al [57] have studied on the effects of QAS and IL, BMIM-BF4 on the It has been suggested that anions of ILs play a leading role in inhibiting gas hydrates thermodynamically, while cations can also contribute to gas hydrate inhibition when specific functional groups, like a hydroxyl group (-OH), are added to them, or their chain length is modified, thus making them able to interact with water molecules [29,31,38,71]. Furthermore, the thermodynamic gas hydrate inhibition efficiency for ILs with the same anion attached to shorter alkyl chain (C 2 ) substituent is better than that of ILs with longer alkyl chain (C 4 ) substituent [10,72].…”

Section: Quaternary Ammonium Saltsmentioning

confidence: 99%

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Review on Application of Quaternary Ammonium Salts for Gas Hydrate Inhibition

Hussain

Husin

2020

Applied Sciences

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Gas hydrate solids occurrence is considered as one of the serious challenges in flow assurance as it affects the hydrocarbon production significantly, especially in deep water gas fields. The most cost-effective method to inhibit the formation of hydrate in pipelines is by injecting a hydrate inhibitor agent. Continuous studies have led to a comprehensive understanding on the use of low dosage hydrate inhibitors such as ionic liquid and quaternary ammonium salts which are also known as dual function gas hydrate inhibitors. This paper covers the latest types of quaternary ammonium salts (2020–2016) and a summary of findings which are essential for future studies. Reviews on the effects of length of ionic liquids alkyl chain, average suppression temperatures, hydrate dissociation enthalpies, and electrical conductivity to the effectiveness of the quaternary ammonium salts as gas hydrate inhibitors are included.

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“…Synthetic gas hydrates can be utilized for gas storage, gas transportation [7,8], desalination [9,10], gas separation [11][12][13], etc. Nonetheless, in the case of gas conveyance through pipelines the formation of gas hydrates must be inhibited in order to prevent blockage [14,15].…”

Section: Introductionmentioning

confidence: 99%

Analysis of the Dissolution of CH4/CO2-Mixtures into Liquid Water and the Subsequent Hydrate Formation via In Situ Raman Spectroscopy

Holzammer

Braeuer

2020

Energies

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We report an experimental study for the investigation into the suitability of hydrate formation processes for the purification of methane (CH 4 ) from carbon dioxide (CO 2 ) at a sub-cooling temperature of 6 K and a pressure of 4 MPa. The experiments were conducted in a stirred batch reactor. Three different initial CH 4 /CO 2 mixtures with methane fractions of 70.1 mol%, 50.3 mol%, and 28.5 mol% were tested. The separation efficiency was quantified by measuring in situ via Raman spectroscopy the ratios of CH 4 /CO 2 in the gas mixture, the liquid water-rich phase before hydrate formation, and the solid hydrate phase after the onset of the hydrate formation. The results indicated that the main separation effect is obtained due to the preferential dissolution of CO 2 into the liquid water-rich phase before the onset of the hydrate formation.Energies 2020, 13, 793 2 of 17 hydrate phase is prone to error, especially if the solubility of the gas species in the liquid water-rich phase, which coexists with the hydrate phase, is high. To the knowledge of the authors, there has been no study that correlates the composition of the CH 4 /CO 2 gas mixture, with the dissolution of CH 4 and CO 2 into the liquid water-rich phase before the hydrate formation and the subsequent incorporation of CH 4 and CO 2 into the solid gas hydrate phase.Raman spectroscopy is one possible method for the remote and in situ measurement of the composition of fluid and solid mixtures and has been applied to the analysis of gas hydrates and fluid mixtures in the context of gas hydrates [26,27].Therefore, the object of this work is to put into context the composition of the gaseous CH 4 /CO 2 -mixture with the dissolution of CH 4 and CO 2 into the liquid water-rich phase before hydrate formation and the incorporation of CH 4 and CO 2 into the solid pure hydrate phase using Raman spectroscopy. Three different initial gas compositions were employed to evaluate the effect of the initial gas composition on the fractions of CH 4 and CO 2 in the vapor phase, the liquid water-rich phase, and the hydrate phase. Finally, CO 2 selectivities relevant for gas separation or gas purification processes are discussed. Materials and Methods MaterialsThe experiments were conducted with deionized water with a conductivity of less than 10 µS/cm and with gaseous premixed binary CH 4 /CO 2 -mixtures (Linde, molar purity 99.5%) with three certificated CH 4 molar fractions of 0.701, 0.503, and 0.285. ApparatusA schematic diagram of the experimental setup is given in Figure 1, which consists of a high-pressure view cell (maximum pressure 25 MPa, internal and non-adjustable volume 26 mL) and a Raman probe.Energies 2020, 13, x FOR PEER REVIEW 2 of 17

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Experimental and computational investigation of methane hydrate inhibition in the presence of amino acids and ionic liquids

Cited by 53 publications

References 55 publications

Chemically Influenced Self-Preservation Kinetics of CH4 Hydrates below the Sub-Zero Temperature

Chemically Influenced Self-Preservation Kinetics of CH4 Hydrates below the Sub-Zero Temperature

Review on Application of Quaternary Ammonium Salts for Gas Hydrate Inhibition

Analysis of the Dissolution of CH4/CO2-Mixtures into Liquid Water and the Subsequent Hydrate Formation via In Situ Raman Spectroscopy

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