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

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.publishedVersio

Dataset for the experimental study of dimethyl sulfoxide as a thermodynamic inhibitor of methane hydrate formation

To determine the ability of dimethyl sulfoxide (DMSO) to inhibit methane hydrate formation by the thermodynamic mechanism, we measured the pressures and temperatures of monovariant equilibrium of three phases: gaseous methane, aqueous DMSO solution, and methane hydrate. A total of 54 equilibrium points were obtained. Hydrate equilibrium conditions have been measured for eight different concentrations of dimethyl sulfoxide ranging from 0 to 55 mass%, at temperatures of 242–289 K and pressures of 3–13 MPa. Measurements were performed in an isochoric autoclave (volume of 600 cm3, inside diameter of 8.5 cm) at a heating rate of 0.1 K/h and intense fluid agitation (600 rpm) with four-blade impeller (diameter of 6.1 cm, blade height of 2 cm). The specified stirring speed for aqueous DMSO solutions at 273–293 K is equivalent to a range of Reynolds numbers of 5.3‧103–3.7‧104. The endpoint of methane hydrate dissociation at defined temperature and pressure values was taken as the equilibrium point. The anti-hydrate activity of DMSO was analyzed on a mass% and mol% scale. Precise correlations between the thermodynamic inhibition effect of dimethyl sulfoxide ΔTh and the influencing factors (DMSO concentration and pressure) were derived. Powder X-ray diffractometry was employed to examine the phase composition of the samples at 153 K. Measurement of ice freezing points in aqueous solutions of dimethyl sulfoxide (up to 50 mass%) at ambient pressure allowed us to clarify the location of the liquidus line in the DMSO-H2O system and to check the hydrate equilibrium data for thermodynamic consistency

Structural and electrical properties of Mg–Cu- and Mg–Cu–Li-doped bismuth niobate semiconductors with the pyrochlore structure

This work studies a series of synthesized Bi$_{1.6}$Mg$_{0.8-x}$Cu$_x$Nb$_{1.6}$O$_{7-\delta}$ ($x$ = 0.2, 0.4) semiconductors and their Lidoped compositions. A detailed structure investigation combining high-resolution neutron-, synchrotron-, and X-ray diffraction methods, as well as DFT calculations, revealed the preferential location of Cu and Li atoms at the Bi sites and Mg atoms at the Nb ones. According to high-temperature X-ray diffraction data, a structural modification caused by the activation of oxygen transport occurs at 200°C. The linear thermal expansion coefficient was found to be 3.6–4.6⋅10$^{−6}$ K$^{−1}$ (50–400°C). Magnetic susceptibility measurements allowed us to determine weak antiferromagnetic exchange interactions. The direct band gap was predicted using the DFTHSE03 hybrid functional calculation, and the optical direct band gap was estimated at 2.3–2.4 eV. Impedance spectroscopy and a dc four-probe technique were also employed to examine the samples$^,$ electrical properties. The high mixed electronic-ionic conductivity of the pyrochlores was detected, while the vacancies created by Lidoping in Bi$_{1.5-y}$Li$_y$Mg$_{0,375}$Cu$_{0,375}$Nb$_{1.5}$O$_{7-\delta}$ have been found not to affect the conductivity. Besides, the pyrochlores are chemically compatible with the La$_{0.7}$Sr$_{0.3}$MnO$_3$ perovskite (up to 800°C). These make us believe that the studied Mg–Cu- and Mg–Cu–Li-doped bismuth niobate semiconductors can become the basis for composite electrodes to boost their oxygen conductivity

Dataset for the phase equilibria and PXRD studies of urea as a green thermodynamic inhibitor of sII gas hydrates

The equilibrium conditions of sII methane/propane hydrates have been experimentally determined for the C3H8/CH4-H2O-urea system. The equilibrium dissociation temperatures and pressures of sII hydrates span a wide P,T-range (266.7–293.9 K; 0.87–9.49 MPa) and were measured by varying the feed mass fraction of urea in solution from 0 to 50 mass%. The experimental points at feed urea concentration ≤ 40 mass% correspond to the V-Lw-H equilibrium (gas-aqueous urea solution-gas hydrate). A four-phase V-Lw-H-Su equilibrium (with an additional phase of solid urea) was observed because the solubility limit of urea in water was reached for all points at a feed mass fraction of 50 mass% and for one point at 40 mass% (266.93 K). Gas hydrate equilibria were measured using a high-pressure rig GHA350 under isochoric conditions with rapid fluid stirring and slow ramp heating of 0.1 K/h. Each measured point represents complete dissociation of the sII hydrate. The phase equilibrium data was compared with the literature reported for the C3H8/CH4-H2O and CH4-H2O-urea systems. A comprehensive analysis of the thermodynamic inhibition effect of urea to sII C3H8/CH4 hydrates on pressure and concentration of the inhibitor was carried out. The phase composition of the samples was analyzed by powder X-ray diffractometry at 173 K

Unusual Self-Preservation of Methane Hydrate in Oil Suspensions

The effect of self-preservation of methane hydrate particles with a characteristic size of a few tens of micrometers was found in suspensions of the hydrate in four crude oils. For example, an ice–hydrate suspension in one of the oils at atmospheric pressure and a temperature of −20 °C loses only 4% of its gas in 5 h. No self-preservation occurs in suspensions of the hydrate in decane with similarly sized hydrate particles. We consider that the observed self-preservation of such small particles is mainly due to the formation of insulating ice shell on the surface of the hydrate particles. Our results show that the adsorbed medium influences the self-preservation of gas hydrates and allows for this phenomenon to be managed

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

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