Effect of solvent swelling on pyrolysis of kerogen (type-I) isolated from Göynük oil shale (Turkey)

Sert, Murat; Ballice, Levent; Yüksel, Mithat; Sağlam, Mehmet; Reimert, R.; Erdem, S.

doi:10.1016/j.jaap.2008.10.022

Cited by 19 publications

(15 citation statements)

References 36 publications

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“…Kerogen was isolated from the whole rock shale sample by a series of acid treatments using methods described in previous kerogen isolation experiments 26 – 30 , 50 . First, the carbonate minerals are removed by treating 2.5 g of shale rock with 30 ml of 5N HCl for 48 hours.…”

Section: Methodsmentioning

confidence: 99%

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Kerogen Swelling and Confinement: Its implication on Fluid Thermodynamic Properties in Shales

Pathak

Kweon

Deo

et al. 2017

Sci Rep

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Type I kerogen was isolated from Green River Shale and characterized using SEM, TGA, DSC, and nitrogen adsorption. The swelling behavior of this kerogen with decane was analyzed using traditional test-tube swelling experiment and Dynamic Light Scattering. The TGA and DSC were used to analyze the thermodynamic behavior of decane that was sorbed in the kerogen and show that kerogen suppresses the boiling point of decane due to the effect of confinement. However, the suppression is larger when oil (a multicomponent mixture) was used, possibly due to the combined effect of differential uptake of components by kerogen (kerogen prefers and sorbs polars and aromatics more than saturates, leading to splitting of oil into a sorbed and a free phase) and confinement in nano pores. Test-tube swelling, TGA, and DSC experiments were also performed on pyridine(polar-aromatic)-swelled kerogen. The combined and individual contributions from the two effects (the effect of confinement and differential uptake of hydrocarbon components) on properties of liquid in contact with kerogen, are studied in this work. Molecular Dynamics (MD) simulations revealed the variation in the swelling of type II kerogen in the presence of same amount of different liquids (differential swelling of kerogen).Kerogen is a complex heterogeneous carbonaceous material, and it is the precursor of oil and gas found in the sub-surface. It is the polymeric material formed by the biogeochemical alteration of detrital and dissolved organic matter that was deposited together with inorganic sediment, and it is the primary source of oil and gas accumulations throughout the world. Kerogen is a key component of shale rocks and plays a key role in the storage and recovery of hydrocarbons from them. Current techniques for the recovery of hydrocarbons from shales leave over 80% of hydrocarbons in the subsurface 1 . Kerogen is the fraction of the organic matter in buried sediments that is insoluble in common solvents. Although kerogen does not dissolve in organic solvents, like insoluble synthetic polymers such as elastomers and other porous materials 2 , it sorbs and is swollen by them. Kerogen is usually classified into four types based on the depositional environment, the biological source of the organic matter from which it was derived and its elemental composition, particularly the H/C and O/C ratios. Type I (predominantly lacustrine) and type II (predominantly marine) kerogens have high H/C and low O/C ratios, and they are capable of generating oil and gas as progressive burial in the subsurface increases their temperature and pressure. Type III (predominately terrestrial) humic kerogen has lower H/C and higher O/C ratios than types I and II. It generates natural gas but little or no oil. Type IV kerogen is the recalcitrant organic matter that has been pyrolyzed, oxidized and/or recycled. It has the lowest H/C and highest O/C ratios of any type of kerogen, and it cannot generate significant amounts of oil or gas. A fifth class, type IIS, sulfur-rich type II kerogen,...

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Section: Methodsmentioning

confidence: 99%

“…Type I kerogen was isolated from the Green River Formation shale sample by series of acid treatments based on previous kerogen isolation procedures 26 – 30 and used in the experiments reported here. The kerogen was extracted from samples collected from the Mahogany zone of Green River Formation, provided by Utah Geological Survey.…”

Section: Introductionmentioning

confidence: 99%

Kerogen Swelling and Confinement: Its implication on Fluid Thermodynamic Properties in Shales

Pathak

Kweon

Deo

et al. 2017

Sci Rep

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“…There have been extensive experiments on the adsorption of gases in shales and kerogens. − However, experiments on gas sorption-induced shale swelling are limited. , The extensive experiments performed on liquid sorption-induced kerogen swelling − have mainly been conducted at room conditions. Larsen et al − have measured swelling of different types of kerogen; the measured swelling is in the range of 10 to 25% in normal pentane ( n -C 5 H 12 ) and normal heptane ( n -C 7 H 16 ).…”

Section: Introductionmentioning

confidence: 99%

Kerogen Swelling in Light Hydrocarbon Gases and Liquids and Validity of Schroeder’s Paradox

Firoozabadi

2021

J. Phys. Chem. C

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Kerogen is often the organic part of the shale and provides the pore space for a large part of the hydrocarbons in place. Kerogen molecules are flexible like polymer molecules, and may swell when in contact with specific solvents. The difference in swelling of a polymer when exposed to a pure liquid versus its saturated vapor is known as Schroeder’s paradox, which has a long history of controversy. To the best of our knowledge, kerogen swelling induced by a hydrocarbon in both gas and liquid states has not been investigated. We investigate the sorption of gaseous and liquid propane, normal butane, and normal pentane in kerogen and kerogen swelling at various pressures. A flexible kerogen matrix is created using molecular dynamics simulations. The large pores are created and maintained with a dummy particle and nailed atoms, respectively. The hydrocarbon sorption and kerogen swelling induced by the sorption of hydrocarbon gases and liquids are investigated by the hybrid molecular dynamics-grand canonical Monte Carlo simulations. Results show that smaller hydrocarbon molecules in both gas and liquid states have higher sorption and induce higher swelling and structural changes in the kerogen matrix. Hydrocarbon liquids have higher sorption and induce higher kerogen swelling than the corresponding gases at saturation pressure in agreement with Schroeder’s paradox. Hydrocarbon gases lead to the moderate kerogen swelling from expansion of large pores; hydrocarbon liquids swell the kerogen more significantly not only by expanding the large pore but also by creating new pores and throats. Liquid-inducing kerogen swelling is accompanied by hydrocarbon dissolution in the kerogen matrix altering significantly the pore surface area, porosity, and pore size distribution. The work sets the stage for further studies considering the effect of production on shale volumetric strain.

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“…Kerogen is the insoluble part of organic material and composed mainly of carbon, hydrogen and oxygen with minor amounts of nitrogen and sulfur. Hydrocarbons are released as vapor when kerogen is subjected to a temperature between 300 and 660 °C in the absence of oxygen [4,5].…”

Section: Introductionmentioning

confidence: 99%

Effect of Mineral Matter on Product Yield and Composition at Isothermal Pyrolysis of Turkish Oil Shales

Sert¹,

Ballice²,

Yüksel³

et al. 2009

Oil Shale

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This study was aimed to investigate the effect of mineral matter of Göynük oil shales (GOS) on pyrolysis and product evolution. Organic part was separated from mineral matter before pyrolysis in an isothermal pyrolysis reactor. In the demineralization step, carbonate, pyrite and silicates were removed from kerogen by using HCl, HNO 3 and HF, respectively. Thereafter all samples were pyrolized in an isothermal pyrolysis apparatus. The temperatures for pyrolysis experiments were 450, 500, 550, 600, 650 °C. Recoveries of volatiles and total hydrocarbons increased with increasing temperature. At pyrolysis of silicate-free oil shale (GOS-F), volatile hydrocarbon recovery (VHR) increased nearly by 10 wt.% as compared with VHR from raw oil shale sample (GOS-R) at each pyrolysis temperature. Carbon content of solid residue was also calculated. The effect of mineral content of oil shale on product yield and composition was determined by establishing carbon balance in the reactor. The amount of solid residue decreased as a function of demineralization degree. The pyrolysis reaction in the presence of silicate mineral showed the catalytic effect of silicate minerals aiding coking reactions, and carbon deposition decreased averagely by 20 wt.% in silicatefree oil shale compared with the value for GOS-R at each temperature.

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Effect of solvent swelling on pyrolysis of kerogen (type-I) isolated from Göynük oil shale (Turkey)

Cited by 19 publications

References 36 publications

Kerogen Swelling and Confinement: Its implication on Fluid Thermodynamic Properties in Shales

Kerogen Swelling and Confinement: Its implication on Fluid Thermodynamic Properties in Shales

Kerogen Swelling in Light Hydrocarbon Gases and Liquids and Validity of Schroeder’s Paradox

Effect of Mineral Matter on Product Yield and Composition at Isothermal Pyrolysis of Turkish Oil Shales

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