Polyvinylsulfonamides as Kinetic Hydrate Inhibitors

Zhang, Qian; Kelland, Malcolm A.; Ajiro, Hiroharu

doi:10.1021/acs.energyfuels.9b04191

Cited by 18 publications

(13 citation statements)

References 33 publications

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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%

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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Section: Chemistrymentioning

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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“…Recently, we have explored polymers without amide groups as KHIs and shown that some polymer classes can give reasonable performance, albeit not as powerful as the best amide-based polymers. − We have also investigated maleic-based amide polymers as KHIs since the monomer maleic anhydride (MA) is a cheap raw material. Maleic-based KHI polymers have been known since the 1990s, but recent advances in structure–activity analysis have led to polymers with improved performance. , For example, the vinyl acetate/MA copolymer in which the anhydride is reacted with a 60:40 mixture of cyclohexylamine/3-di- n -butylaminopropylamine [VA:MA-60%cHex-40%DBAPA, M n = 11 kg/mol, 25 wt % in 2-butoxyethanol (nBGE)] gave a significantly better performance than previously reported maleamide polymers (also in nBGE) or PVCap (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Non-Amide Polymers as Kinetic Hydrate Inhibitors─Maleic Acid/Alkyl Acrylate Copolymers and the Effect of pH on Performance

2021

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Kinetic hydrate inhibitors (KHIs) have been used for over 25 years to prevent gas hydrate formation in oil and gas production flow lines. The main component in KHI formulations is a water-soluble polymer with many amphiphilic groups, usually made up of amide groups and adjacent hydrophobic groups with 3–6 carbon atoms. KHI polymers are one of the most expensive oilfield production chemicals. Therefore, methods to make cheaper but effective KHIs could improve the range of applications. Continuing earlier work from our group with maleic-based polymers, here, we explore maleic acid/alkyl acrylate copolymers as potential low-cost KHIs. Performance experiments were conducted under high pressure with a structure II-forming natural gas mixture in steel rocking cells using the slow (1 °C/h) constant cooling test method. Under typical pipeline conditions of pH (4–6), the performance of the maleic acid/alkyl acrylate copolymers (alkyl = iso-propyl, iso-butyl, n-butyl, tetrahydrofurfuryl, and cyclohexyl) was poor. However, good performance was observed at very high pH (13–14) due to the thermodynamic effect from added salts in the aqueous phase and the removal of CO2 from the gas phase. A methyl maleamide/n-butyl acrylate copolymer gave very poor performance, giving evidence that direct bonding of the hydrophilic amide and C4 hydrophobic groups is needed for good KHI performance. Reaction of the maleic anhydride (MA) units in MA/alkyl acrylate 1:1 copolymers with dibutylaminopropylamine or dibutylaminoethanol gave polymers with good KHI performance, with MA/tetrahydrofurfuryl methacrylate being the best. Oxidation of the pendant dibutylamino groups to amine oxide groups improved the performance further, better than poly(N-vinyl caprolactam).

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“…This SNG composition is given in Table . We used our standard slow constant-cooling (SCC) test method, which we have used in many previous studies with this equipment. − This allows the reader to compare the results to many other classes of additives tested in our laboratories. A study recently showed that the slow ramped cooling experiments gave good reproducibility and recommended lowering the temperature by 0.5 °C every 3 h .…”

Section: Methodsmentioning

confidence: 99%

A Simple and Direct Route to High-Performance Acrylamido-Based Kinetic Gas Hydrate Inhibitors from Poly(acrylic acid)

2020

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(Meth)acrylamido-based polymers are used commercially in kinetic hydrate inhibitor formulations to prevent gas hydrate formation in upstream oil and gas flow lines. The monomers used to make these polymers are relatively expensive. We have now synthesized a series of acrylamido-based polymers directly from low molecular weight poly(acrylic acid) (PAA) in a high-yield process, avoiding the use of expensive monomers. Cloud points of the polymers made from PAA were similar to the homopolymers made from the acrylamido monomers, indicating a good conversion from the acid to the amide group. Slow constant-cooling KHI screening tests were carried out on the new polymers in a series of steel rocking cells using a structure II-forming natural gas mixture. Poly(N-isopropylacrylamide), poly(N-(n-propyl) acrylamide), and polyacryloylpyrrolidine prepared directly from PAA all gave an excellent KHI performance, comparable to the homopolymers made from the acrylamido monomers. This direct synthesis method also allows for a very controlled comparison of the activity of the acrylamido functional groups because every polymer can be derived from the same PAA starting material. Thus, the number of monomer units in each homopolymer is kept constant. Conversion of the poly(methacrylic acid) or poly(methyl methacrylate) by the reaction with amines to give the methacrylamido polymers was not successful, probably due to the steric effect of the backbone methyl groups.

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Polyvinylsulfonamides as Kinetic Hydrate Inhibitors

Cited by 18 publications

References 33 publications

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

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

Non-Amide Polymers as Kinetic Hydrate Inhibitors─Maleic Acid/Alkyl Acrylate Copolymers and the Effect of pH on Performance

A Simple and Direct Route to High-Performance Acrylamido-Based Kinetic Gas Hydrate Inhibitors from Poly(acrylic acid)

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