Advances in the Study of Gas Hydrates by Dielectric Spectroscopy

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.publishedVersio

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

Effective Inhibition of Carbon Steel Corrosion by Waterborne Polyurethane Based on N-tert-Butyl Diethanolamine in 2M HCl: Experimental and Computational Findings

The efficiency of corrosion inhibition for waterborne polyurethane based on N-tert-butyl diethanolamine (tB-WPU) is investigated using different techniques. Corrosion weight loss, open circuit potential experiments, electrochemical impedance spectroscopy, and potentiodynamic polarization measurements show that both a commercial reagent and a polyurethane-based inhibitor prevent corrosion at increasing temperature to 50 °C. At 75 °C, the activity of both reagents is reduced. In stirring conditions, the effectiveness of acid corrosion inhibition (25 °C, 500 ppm) drops abruptly from 89.5% to 60.7%, which is related presumably to the complexity of binding the polymer molecules to the metal surface. As follows from thermodynamic calculations, the adsorption of tB-WPU on the metal surface in 2M HCl can be treated as a physisorption. Model quantum–chemical calculations support the experimental studies and elucidate the nature of steel surface–inhibitor molecule chemical bond, which is realized mainly by carboxyl and amino groups. It is concluded that WPUs can be considered as a perspective alternative to commercial oilfield reagents due to their versatility

Influence of Water Saturation, Grain Size of Quartz Sand and Hydrate-Former on the Gas Hydrate Formation

The development of technologies for the accelerated formation or decomposition of gas hydrates is an urgent topic. This will make it possible to utilize a gas, including associated petroleum one, into a hydrate state for its further use or to produce natural gas from hydrate-saturated sediments. In this work, the effect of water content in wide range (0.7–50 mass%) and the size of quartz sand particles (porous medium; <50 μm, 125–160 μm and unsifted sand) on the formation of methane and methane-propane hydrates at close conditions (subcooling value) has been studied. High-pressure differential scanning calorimetry and X-ray computed tomography techniques were employed to analyze the hydrate formation process and pore sizes, respectively. The exponential growth of water to hydrate conversion with a decrease in the water content due to the rise of water–gas surface available for hydrate formation was revealed. Sieving the quartz sand resulted in a significant increase in water to hydrate conversion (59% for original sand compared to more than 90% for sieved sand). It was supposed that water suction due to the capillary forces influences both methane and methane-propane hydrates formation as well with latent hydrate forming up to 60% either without a detectable heat flow or during the ice melting. This emphasizes the importance of being developed for water–gas (ice–gas) interface to effectively transform water into the hydrate state. In any case, the ice melting (presence of thawing water) may allow a higher conversion degree. Varying the water content and the sand grain size allows to control the degree of water to hydrate conversion and subcooling achieved before the hydrate formation. Taking into account experimental error, the equilibrium conditions of hydrates formation do not change in all studied cases. The data obtained can be useful in developing a method for obtaining hydrates under static conditions

Vendor selection information system on the electronic trading platform for energy supply companies

The main challenges for industrial companies today are to improve the competitiveness of their products and to adapt and respond quickly to changes in the external environment. Ensuring the effective functioning of an industrial enterprise is largely determined by its procurement activities, including the reliability and consistency of the procurement process. Relevance of the topic is conditioned by the fact that procurement is one of the main components in increasing of competitiveness and efficiency of the enterprise, as the major part of costs in the cost price of the finished products is concentrated exactly in procurement. Reducing costs in procurement is one of the ways to improve the efficiency of the enterprise. This advantage can be achieved through the introduction of modern information technologies, namely automation of the process of selecting suppliers on an electronic trading platform. For this purpose, an information system for selecting suppliers on the electronic trading platform has been developed, which enables a more transparent, fast, profitable and less costly selection of the cheapest and most suitable goods for the operation of energy supplying enterprises. Procurement activities are aimed at ensuring that the energy-supplying undertaking receives the right quantity and quality of raw materials, materials, goods and services at the right time, in the right place, from a reliable and trustworthy supplier with good service and at a favourable price. Automating the supplier selection process on an electronic platform is essential in today's market environment

INVESTIGATION OF DYNAMIC CHARACTERISTICS OF ELEMENTS OF AUTOMATICS OF A SMART HOUSE IN PARAMETRICAL STRUCTURAL SCHEMES

Subject: automation of calculation of dynamic characteristics of the device being designed in the system of conceptual design of sensor equipment, structurally-parametric models of dynamic processes and algorithms for the automated calculation of the qualitative characteristics of elements of the information-measuring and control systems (IMCS). The stage of conceptual design most fully determines the operational characteristics of technical systems. However, none of the information support systems of this stage provides an opportunity to evaluate the performance characteristics of the element being designed taking into account its dynamic characteristics. Research objectives: increasing the effectiveness of the evaluation of dynamic characteristics of sensitive elements of the information-measuring and control systems of a smart house. Materials and methods: when solving the problems posed, the mathematical apparatus of system modeling was used (in particular, the energy-information method of modeling processes of various physical nature that occur in the sensor equipment); the main provisions of the theory of automatic control, the theory of constructing computer-aided design systems, the theory of operational calculus; basics of conceptual design of elements of the information-measuring and control systems. Results: we compared the known automated systems for conceptual design of sensors, highlighted their advantages and disadvantages and we showed that none of these systems allows us to investigate dynamic characteristics of the element being designed in a simple and understandable for engineer form. The authors proposed using energy-information method of modeling for the synthesis of operation principles of sensors and analysis of their dynamic characteristics. We considered elementary dynamic chains and issues of synthesis of parametrical structural schemes that reflect the dynamics of the process with the use of mathematical apparatus of operational calculus. We developed the project of automated system of the conceptual design of the sensor equipment that allowed us to visualize construction of the parametrical structural schemes and representation of evaluation results of the dynamic characteristics. Conclusions: it was shown that the energy-information models of chains of various physical nature can be used for synthesis of parametrical structural schemes with dynamic links. The mathematical apparatus was developed for evaluation of dynamic characteristics of parametrical structural schemes in analytic form. We also presented the information flow diagram and the functional model of the subsystem of synthesis of sensor operation principals with allowance for dynamic characteristics

Effective Inhibition of Carbon Steel Corrosion by Waterborne Polyurethane Based on N-<i>tert</i>-Butyl Diethanolamine in 2M HCl: Experimental and Computational Findings

The efficiency of corrosion inhibition for waterborne polyurethane based on N-tert-butyl diethanolamine (tB-WPU) is investigated using different techniques. Corrosion weight loss, open circuit potential experiments, electrochemical impedance spectroscopy, and potentiodynamic polarization measurements show that both a commercial reagent and a polyurethane-based inhibitor prevent corrosion at increasing temperature to 50 °C. At 75 °C, the activity of both reagents is reduced. In stirring conditions, the effectiveness of acid corrosion inhibition (25 °C, 500 ppm) drops abruptly from 89.5% to 60.7%, which is related presumably to the complexity of binding the polymer molecules to the metal surface. As follows from thermodynamic calculations, the adsorption of tB-WPU on the metal surface in 2M HCl can be treated as a physisorption. Model quantum–chemical calculations support the experimental studies and elucidate the nature of steel surface–inhibitor molecule chemical bond, which is realized mainly by carboxyl and amino groups. It is concluded that WPUs can be considered as a perspective alternative to commercial oilfield reagents due to their versatility

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