Molecular insights into the kinetic hydrate inhibition performance of Poly(N-vinyl lactam) polymers

Liu, Jinxiang; Wang, Hongbo; Guo, Jinghua; Chen, Gang; Zhong, Jie; Yan, Youguo; Zhang, Jun

doi:10.1016/j.jngse.2020.103504

Cited by 37 publications

(19 citation statements)

References 48 publications

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“…The data obtained on the dielectric behavior of the systems under consideration speak in favor of the involvement of the inhibitor in hydrogen bonding, which disrupts the local ordering of water molecules and prevents hydrate formation. This mechanism of action of poly (N-vinyl caprolactam) is also supported by calculations [ 45 ].…”

Section: Resultssupporting

confidence: 64%

Advances in the Study of Gas Hydrates by Dielectric Spectroscopy

et al. 2021

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The influence of kinetic hydrate inhibitors on the process of natural gas hydrate nucleation was studied using the method of dielectric spectroscopy. The processes of gas hydrate formation and decomposition were monitored using the temperature dependence of the real component of the dielectric constant ε′(T). Analysis of the relaxation times τ and activation energy ΔE of the dielectric relaxation process revealed the inhibitor was involved in hydrogen bonding and the disruption of the local structures of water molecules.

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Section: Resultssupporting

confidence: 64%

Advances in the Study of Gas Hydrates by Dielectric Spectroscopy

et al. 2021

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“…The presence of salt fragments and PEG residue contributes to an increase in the solubility of polyurethanes in an aqueous medium and facilitates an additional interaction with water molecules through hydrogen bonds disturbing the local water structuring. This is one of the key factors in kinetic gas hydrates inhibition [36,37]. In addition, two more advantages of the developed inhibitors should be noted.…”

Section: Chemistrymentioning

confidence: 99%

“…For example, for polyurethanes with an n-butyl fragment, the statistically significant decrease of T o value from 7.4 ± 0.4 • C for WPU-3 to 5.7 ± 0.5 • C for WPU-6 occurs. The reason for this enhancement in the inhibition efficacy may lie both in the additional interaction of alkyl hydrophobic groups with open hydrate cavities on the crystal surface (crystal growth inhibition), and in perturbing the local water structure by the WPU involvement in hydrogen bonding (nucleation inhibition) [20,37,[41][42][43]. However, unlike the commercial reagent P(VCap-VP), an increase in the concentration of polyurethanes from 0.25 wt% to 0.5 wt% did not give much improvement to their inhibiting power.…”

Section: Interfacial Tension Studymentioning

confidence: 99%

Performance of Waterborne Polyurethanes in Inhibition of Gas Hydrate Formation and Corrosion: Influence of Hydrophobic Fragments

et al. 2020

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The design of new dual-function inhibitors simultaneously preventing hydrate formation and corrosion is a relevant issue for the oil and gas industry. The structure-property relationship for a promising class of hybrid inhibitors based on waterborne polyurethanes (WPU) was studied in this work. Variation of diethanolamines differing in the size and branching of N-substituents (methyl, n-butyl, and tert-butyl), as well as the amount of these groups, allowed the structure of polymer molecules to be preset during their synthesis. To assess the hydrate and corrosion inhibition efficiency of developed reagents pressurized rocking cells, electrochemistry and weight-loss techniques were used. A distinct effect of these variables altering the hydrophobicity of obtained compounds on their target properties was revealed. Polymers with increased content of diethanolamine fragments with n- or tert-butyl as N-substituent (WPU-6 and WPU-7, respectively) worked as dual-function inhibitors, showing nearly the same efficiency as commercial ones at low concentration (0.25 wt%), with the branched one (tert-butyl; WPU-7) turning out to be more effective as a corrosion inhibitor. Commercial kinetic hydrate inhibitor Luvicap 55 W and corrosion inhibitor Armohib CI-28 were taken as reference samples. Preliminary study reveals that WPU-6 and WPU-7 polyurethanes as well as Luvicap 55 W are all poorly biodegradable compounds; BODt/CODcr (ratio of Biochemical oxygen demand and Chemical oxygen demand) value is 0.234 and 0.294 for WPU-6 and WPU-7, respectively, compared to 0.251 for commercial kinetic hydrate inhibitor Luvicap 55 W. Since the obtained polyurethanes have a bifunctional effect and operate at low enough concentrations, their employment is expected to reduce both operating costs and environmental impact.

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“…KHIs can adsorb and bind to these cage surfaces and inhibit the growth of these cages . The interactions between the different sized lactam-based KHIs with open hydrate cages have been studied . It was observed that the carbonyl oxygen on the small lactam-based KHIs (five- and six-ring, e.g., PVP and PVPip) can form only one hydrogen bond with the water molecules in the hydrate cages in the solution.…”

Section: Khis Based On Cyclic Amidesmentioning

confidence: 99%

Review of Kinetic Hydrate Inhibitors Based on Cyclic Amides and Effect of Various Synergists

Singh

Suri

2021

Energy Fuels

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This Review presents a comprehensive literature review of an important class of kinetic hydrate inhibitors (KHIs) that is based on cyclic amides (lactams). The major aspects of the KHIs, such as their synthesis, inhibition mechanism, toxicity, biodegradability, performance, and cloud point, are thoroughly discussed. Data for 70 KHIs made of homo/co/terpolymers from 330 experiments are collected and evaluated for performance. The effects of the inhibitor concentration, molecular weight, monomer ratio of the co/terpolymers, and 35 different synergist chemicals on various KHIs are also studied. In conclusion, the top 10 KHIs with the highest performances that had a cloud point above 70 °C are presented. The copolymer (1:1) N-vinylpyrrolidone/N-vinyl-caprolactam (VP/VCap) is found to have the highest induction time (IT) of 13 to 14 h at 0.25 wt % and at a cooling rate of 1 °C/h. Some KHIs like Inhibex BIO-800 and poly(N-vinyl azacyclooctanone) (PVACO) also have a very high ITs (17 and 13.5 h, respectively) at 0.25 wt % and at a cooling rate of 1 °C/h, but they have low cloud points (<25 °C). Guanidinium salts (n-Bu6GuanCl/n-Bu6GuanBr) and a phosphonium salt, (n-Pe)4PBr, are found to be the best synergists for the cyclic-amide-based KHIs. When used at 0.15 to 0.30 wt % along with the KHIs, they further increase the IT by 3–5 h.

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Molecular insights into the kinetic hydrate inhibition performance of Poly(N-vinyl lactam) polymers

Cited by 37 publications

References 48 publications

Advances in the Study of Gas Hydrates by Dielectric Spectroscopy

Advances in the Study of Gas Hydrates by Dielectric Spectroscopy

Performance of Waterborne Polyurethanes in Inhibition of Gas Hydrate Formation and Corrosion: Influence of Hydrophobic Fragments

Review of Kinetic Hydrate Inhibitors Based on Cyclic Amides and Effect of Various Synergists

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