Термодинамические условия образования гидратов метана при промысловой транспортировке попутного нефтяного газа

Статья в Elpub

Территория «НЕФТЕГАЗ». 2019; : 54-66

Термодинамические условия образования гидратов метана при промысловой транспортировке попутного нефтяного газа

Аннотация

В статье проанализирована термодинамика гидратообразования с использованием комбинации уравнения состояния типа Cubic Plus Association и модели Ван-дер-Ваальса – Платтье. По результатам анализа авторами предложено уточненное уравнение состояния типа Cubic Plus Association для бинарной смеси «вода – метан», где физические взаимодействия молекул описываются уравнением Пенга – Робинсона, а ассоциирующие, возникающие в результате водородных связей молекул воды – термодинамической теорией возмущений. Молекулярная структура воды рассматривается в виде комбинации структур двух типов, первый из которых сформирован в виде крупных упорядоченных ассоциатов, в которых каждая молекула воды образует четыре водородные связи (кластер). Второй тип структур – неупорядоченные молекулы, окружающие кластеры. Проведены корреляции для оценки энергетического параметра физических взаимодействий молекул воды для упорядоченных водных ассоциатов, а также в целях оценки мольных долей воды в бинарной смеси компонентов, вступивших и не вступивших в ассоциационные взаимодействия. Для молекул неполярных компонентов и неупорядоченных молекул воды уравнение состояния сведено к классическому виду уравнения состояния Пенга – Робинсона.

В статье также представлена разработанная авторами методика прогнозирования гидратообразования при транспортировке попутного нефтяного газа, основанная на принципах термодинамического фазового равновесия системы «гидрат – жидкость – газ», в которой критерием гидратообразования служит термодинамический баланс коэффициентов летучести воды в жидкой, газообразной и твердой фазах. В целях повышения точности расчета коэффициента фугитивности (летучести) «пустой» гидратной решетки введен новый поправочный коэффициент. Для оценки применимости методики прогнозирования гидратообразования проведено сопоставление расчетной зависимости давления гидратообразования от температуры с экспериментальными данными, полученными при разных термобарических условиях.

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Territorija “NEFTEGAS” [Oil and Gas Territory]. 2019; : 54-66

Thermodynamical Conditions of Methane Hydrate Formation during Field Transportation of Associated Petroleum Gas

Mikhaylov V. G., Khalfin R. S.

Abstract

A combination of cubic-plus-association equation of state and the van der Waals – Platteeuw model was employed for the description of the hydrate formation thermodynamics. Based on the analysis results, the authors proposed a refined equation of state of the cubic-plus-association type for water-containing mixtures where the physical contributions are represented by the Peng – Robinson equation and the chemical contributions from hydrogen bonding of water are described by the thermodynamic perturbation theory. The molecular structure of water is represented as a combination of two types of structures. The first type of structure is formed as a pair of ordered associates with four hydrogen bonds (cluster). The second type is disordered molecules that surround clusters. For ordered water associates, a correlation is obtained for estimating the energy parameter of the physical interactions of water molecules, as well as a correlation for estimating the molar fractions of water in a binary mixture of components that have entered and have not entered into association interactions. For molecules of non-polar components and disordered water molecules, the equation of state reduces to the classical form of Peng – Robinson equation of state.

The article also presents a method for predicting hydrate formation during associated petroleum gas transportation, which has been developed by the authors, based on the principles of thermodynamic phase hydration-liquid – gas equilibrium, in which the thermodynamic balance of water volatility in liquid, gaseous and solid phases serves as a criterion for hydrate formation. In order to improve the accuracy of calculation of the fugacity factor of the “empty” hydrate lattice, a new correction factor was introduced. To assess the applicability of the hydrate formation prediction technique, the calculated dependence of the hydrate formation pressure on temperature is compared with experimental data obtained under different temperature and pressure conditions.

References