Tag: equilibrium thermodynamics

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THERMODYNAMICS OF TYPE II KEROGEN TRANSFORMATION

Home > Archive > No. 3 (180) 2019 > 25-40

Geology & Geochemistry of Combustible Minerals No. 3 (180) 2019, 25-40.

https://doi.org/10.15407/ggcm2019.03.025

Yuri Khokha, Oleksandr Lyubchak, Myroslava Yakovenko

Institute of Geology and Geochemistry of Combustible Minerals of National Academy of Sciences of Ukraine, Lviv,
e-mail: igggk@mail.lviv.ua

Abstract

The article reviews the chemical structure of type II kerogen. The changes that occur with the structure of type II kerogen as it passes through the stages of catagenesis from immature to post-mature are evaluated. Structural models of type II kerogen at different stages of catagenesis are presented: both obtained empirically after studying the structure by physical and chemical methods and the results of modelling by molecular dynamics method.

Methods of equilibrium thermodynamics are used to calculate the composition of the kerogen–gas system for crust sections in the range of 1–20 km with a heat flux of 40 to 100 mW/m2. The composition of kerogen/fluid geochemical system is calculated using the E. T. Jaynes formalism. It boils down to determining the optimal distribution of 5 elements (C, H, O, N, S) among the 44 additive constituents of the solid phase (i. e., type II kerogen) and other individual components that are included in the system (CO2, H2O, H2S, NH3, CH4, C2H6, C3H8, i-C4H10, n-C4H10, i-C5H12, neo-C5H12, n-C5H12).

Comparison with the experiments showed that the results of the calculations do not contradict the experiments, with study the structure and changes in type II kerogen with increasing degree of catagenesis. In the analysis of changes in the concentrations of water, carbon dioxide and hydrogen sulfide, it is founded that kerogen could be not only a donor of atoms for gas components, but also their acceptor in contact with a high-energy fluid stream. It is shown that the determination of sulfur-containing atomic groups of kerogen by thermodynamic modelling yields gives more reliable results than molecular dynamics methods.

Established is that the concept of “methane-graphite death”, which takes place in the state of thermodynamic equilibrium in the transformation of organic matter, is erroneous. The calculation shows that the composition of the kerogen–gas system, in addition to methane and carbon, includes solid-phase heteroatom groups, various additive components of aromatic structures and gases, both organic and inorganic. The distribution of elements between the additive components of kerogen and gases in this system controls the pressure and temperature in a complex way. The nature of changes in hydrocarbon gas concentrations in equilibrium with type II kerogen indicates the presence of an “oil window” in low-warmed zones within 2–4 km depths.

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Keywords

type II kerogen, catagenesis, “oil window”, equilibrium thermodynamics, Jaynes formalism.

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EFFECT OF TEMPERATURE FLOW ON GAS-GENERATING POTENTIAL OF HUMIC ACIDS OF ORGANIC MATTER

Home > Archive > No. 3-4 (176-177) 2018 > 49-62

Geology & Geochemistry of Combustible Minerals No. 3-4 (176-177) 2018, 49-62.

Yuri KHOKHA, Oleksandr LYUBCHAK, Myroslava YAKOVENKO

Institute of Geology and Geochemistry of Combustible Minerals of National Academy of Sciences of Ukraine, Lviv, e-mail: igggk@mail.lviv.ua

Abstract

Experiments on artificial “maturation” of humic acids, kerogen, model compounds of organic compounds and individual hydrocarbons up to 4000 hours carried out in a wide range of pressures and temperatures were considered. An analysis of trends in the change in the composition of gases over time, which was formed during experiments, was carried out. It is concluded that in the considered experiments the state of thermodynamic equilibrium is not achieved; they only show tendencies in the changes of the solid, liquid and gas phase. A method for simulating artificial maturation of organic compounds in the process of catagenesis, based on the Jaynes formalism, was developed. An equilibrium concentration of gases in contact with a humic substance depending on temperature is calculated. The results of the calculation are in good correspondence with the trends shown by experimental studies.

Full Text

Keywords

gas-generation, humic acids, catagenesis, Jaynes formalism, equilibrium thermodynamics.

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