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Title: Reactive Molecular Dynamics Simulation of Kerogen Thermal Maturation and Cross-Linking Pathways

Abstract

For this study, molecular dynamics simulations were performed with a ReaxFF reactive force field to investigate bond breaking and bond formation mechanisms during the early thermal maturation of kerogen and potential crosslinking pathways towards a three-dimensional (3D) quasi-infinite molecular network (crosslinked kerogen). Starting with small ensembles of high molecular mass models for immature type I Green River Shale kerogen (Kerogen 1-I), top of the oil window type II kerogen (Kerogen 2-L), and low maturity type III kerogen (Kerogen 3-L), low molecular mass species including H2O, H2S, C2H4, C3H6 were produced as the maturities of the remaining kerogens increased. Highly reactive fragments, which are not detected in pyrolysis experiments, were also produced. Further, the crosslinking mechanism in the newly develop polymeric kerogen networks appears to be highly complex and it is influenced by the nature of the kerogen. Covalent —C—S—, —C—O— and —C—C— bonds are the primary crosslinks that structurally binds kerogen monomers together. The trends observed in the thermochemical transformation of kerogen and the kerogen crosslinking pathways are consistent with the theoretical and experimental studies reported in the scientific literature. The reactive force field molecular dynamics simulation provides a potentially valuable alternative approach to the development of a realistic 3Dmore » molecular network of kerogen. However, the conversion of kerogen molecules into a 3D molecular network was low.« less

Authors:
ORCiD logo [1];  [2];  [1]
  1. Idaho National Lab. (INL), Idaho Falls, ID (United States)
  2. Temple Univ., Philadelphia, PA (United States)
Publication Date:
Research Org.:
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE); USDOE Laboratory Directed Research and Development (LDRD) Program
Contributing Org.:
Boise State Univ., ID (United States); Pennsylvania State Univ., University Park, PA (United States)
OSTI Identifier:
1414450
Report Number(s):
INL/JOU-17-41419
Journal ID: ISSN 0887-0624
Grant/Contract Number:  
AC07-05ID14517
Resource Type:
Accepted Manuscript
Journal Name:
Energy and Fuels
Additional Journal Information:
Journal Volume: 31; Journal Issue: 11; Journal ID: ISSN 0887-0624
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
04 OIL SHALES AND TAR SANDS; 02 PETROLEUM; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Kerogen Crosslinking; Reactive Molecular Dynamics

Citation Formats

Pawar, Gorakh, Meakin, Paul, and Huang, Hai. Reactive Molecular Dynamics Simulation of Kerogen Thermal Maturation and Cross-Linking Pathways. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.energyfuels.7b01555.
Pawar, Gorakh, Meakin, Paul, & Huang, Hai. Reactive Molecular Dynamics Simulation of Kerogen Thermal Maturation and Cross-Linking Pathways. United States. https://doi.org/10.1021/acs.energyfuels.7b01555
Pawar, Gorakh, Meakin, Paul, and Huang, Hai. Wed . "Reactive Molecular Dynamics Simulation of Kerogen Thermal Maturation and Cross-Linking Pathways". United States. https://doi.org/10.1021/acs.energyfuels.7b01555. https://www.osti.gov/servlets/purl/1414450.
@article{osti_1414450,
title = {Reactive Molecular Dynamics Simulation of Kerogen Thermal Maturation and Cross-Linking Pathways},
author = {Pawar, Gorakh and Meakin, Paul and Huang, Hai},
abstractNote = {For this study, molecular dynamics simulations were performed with a ReaxFF reactive force field to investigate bond breaking and bond formation mechanisms during the early thermal maturation of kerogen and potential crosslinking pathways towards a three-dimensional (3D) quasi-infinite molecular network (crosslinked kerogen). Starting with small ensembles of high molecular mass models for immature type I Green River Shale kerogen (Kerogen 1-I), top of the oil window type II kerogen (Kerogen 2-L), and low maturity type III kerogen (Kerogen 3-L), low molecular mass species including H2O, H2S, C2H4, C3H6 were produced as the maturities of the remaining kerogens increased. Highly reactive fragments, which are not detected in pyrolysis experiments, were also produced. Further, the crosslinking mechanism in the newly develop polymeric kerogen networks appears to be highly complex and it is influenced by the nature of the kerogen. Covalent —C—S—, —C—O— and —C—C— bonds are the primary crosslinks that structurally binds kerogen monomers together. The trends observed in the thermochemical transformation of kerogen and the kerogen crosslinking pathways are consistent with the theoretical and experimental studies reported in the scientific literature. The reactive force field molecular dynamics simulation provides a potentially valuable alternative approach to the development of a realistic 3D molecular network of kerogen. However, the conversion of kerogen molecules into a 3D molecular network was low.},
doi = {10.1021/acs.energyfuels.7b01555},
journal = {Energy and Fuels},
number = 11,
volume = 31,
place = {United States},
year = {2017},
month = {9}
}

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Works referenced in this record:

Kerogen origin, evolution and structure
journal, May 2007


Microorganisms persist at record depths in the subseafloor of the Canterbury Basin
journal, January 2014

  • Ciobanu, Maria-Cristina; Burgaud, Gaëtan; Dufresne, Alexis
  • The ISME Journal, Vol. 8, Issue 7
  • DOI: 10.1038/ismej.2013.250

A metagenomic window into carbon metabolism at 3 km depth in Precambrian continental crust
journal, September 2015

  • Magnabosco, Cara; Ryan, Kathleen; Lau, Maggie C. Y.
  • The ISME Journal, Vol. 10, Issue 3
  • DOI: 10.1038/ismej.2015.150

Effects of organic matter heterogeneity on sorption and desorption of organic contaminants by soils and sediments
journal, July 2003


Impacts of Heterogeneous Organic Matter on Phenanthrene Sorption:  Equilibrium and Kinetic Studies with Aquifer Material
journal, February 2000

  • Karapanagioti, Hrissi K.; Kleineidam, Sybille; Sabatini, David A.
  • Environmental Science & Technology, Vol. 34, Issue 3
  • DOI: 10.1021/es9902219

Black Carbon and Kerogen in Soils and Sediments. 2. Their Roles in Equilibrium Sorption of Less-Polar Organic Pollutants
journal, November 2004

  • Xiao, Baohua; Yu, Zhiqiang; Huang, Weilin
  • Environmental Science & Technology, Vol. 38, Issue 22
  • DOI: 10.1021/es049761i

Chemical modelling of kerogens
journal, January 1987


Realistic molecular model of kerogen’s nanostructure
journal, February 2016

  • Bousige, Colin; Ghimbeu, Camélia Matei; Vix-Guterl, Cathie
  • Nature Materials, Vol. 15, Issue 5
  • DOI: 10.1038/nmat4541

Three-Dimensional Structure of the Siskin Green River Oil Shale Kerogen Model: A Comparison between Calculated and Observed Properties
journal, January 2013

  • Orendt, Anita M.; Pimienta, Ian S. O.; Badu, Shyam R.
  • Energy & Fuels, Vol. 27, Issue 2
  • DOI: 10.1021/ef3017046

Molecular Modeling of the Volumetric and Thermodynamic Properties of Kerogen: Influence of Organic Type and Maturity
journal, December 2014

  • Ungerer, Philippe; Collell, Julien; Yiannourakou, Marianna
  • Energy & Fuels, Vol. 29, Issue 1
  • DOI: 10.1021/ef502154k

Raman spectroscopy of carbon and solid bitumens in sedimentary and metamorphic rocks
journal, August 2003

  • Jehlička, Jan; Urban, Ondřej; Pokorný, Jan
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 59, Issue 10
  • DOI: 10.1016/S1386-1425(03)00077-5

Direct Characterization of Kerogen by X-ray and Solid-State 13 C Nuclear Magnetic Resonance Methods
journal, May 2007

  • Kelemen, S. R.; Afeworki, M.; Gorbaty, M. L.
  • Energy & Fuels, Vol. 21, Issue 3
  • DOI: 10.1021/ef060321h

Initial Pyrolysis Mechanism of Oil Shale Kerogen with Reactive Molecular Dynamics Simulation
journal, April 2015


Chemical structure and 13C NMR spectra of the kerogen of carbonaceous rock masses
journal, February 2010

  • Bushnev, D. A.; Burdel’naya, N. S.; Mokeev, M. V.
  • Doklady Earth Sciences, Vol. 430, Issue 2
  • DOI: 10.1134/S1028334X10020145

Computer simulation of the molecular structure of bituminous coal
journal, November 1992


Structural study of the Moroccan Timahdit (Y-layer) oil shale kerogen using chemical degradations
journal, April 2001


The neutron scattering length density of kerogen and coal as determined by CH3OH/CD3OH exchange
journal, January 2014


Subcontinuum mass transport of condensed hydrocarbons in nanoporous media
journal, April 2015

  • Falk, Kerstin; Coasne, Benoit; Pellenq, Roland
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7949

A molecular dynamics study of natural organic matter: 1. Lignin, kerogen and soot
journal, November 2009


The dynamics of hydraulic fracture water confined in nano-pores in shale reservoirs
journal, March 2015

  • Hu, Yinan; Devegowda, Deepak; Striolo, Alberto
  • Journal of Unconventional Oil and Gas Resources, Vol. 9
  • DOI: 10.1016/j.juogr.2014.11.004

Dynamic interactions of natural organic matter and organic compounds
journal, March 2012


Preparation and characterization of humic acid cross-linked with organic bridging groups
journal, June 2012


The effect of cross linking density on the mechanical properties and structure of the epoxy polymers: molecular dynamics simulation
journal, June 2013


Predicting oil and gas compositional yields via chemical structure–chemical yield modeling (CS-CYM): Part 1 – Concepts and implementation
journal, February 2007


Molecular simulation and modelisation of methane/ethane mixtures adsorption onto a microporous molecular model of kerogen under typical reservoir conditions
journal, October 2014


Effect of Chain Length and Pore Accessibility on Alkane Adsorption in Kerogen
journal, November 2015


Molecular concept and experimental evidence of competitive adsorption of H2O, CO2 and CH4 on organic material
journal, January 2014


Kukersite oil shale kerogen solvent swelling in binary mixtures
journal, March 2013


ReaxFF:  A Reactive Force Field for Hydrocarbons
journal, October 2001

  • van Duin, Adri C. T.; Dasgupta, Siddharth; Lorant, Francois
  • The Journal of Physical Chemistry A, Vol. 105, Issue 41
  • DOI: 10.1021/jp004368u

Combustion of an Illinois No. 6 coal char simulated using an atomistic char representation and the ReaxFF reactive force field
journal, March 2012


Mechanism and Kinetics for the Initial Steps of Pyrolysis and Combustion of 1,6-Dicyclopropane-2,4-hexyne from ReaxFF Reactive Dynamics
journal, May 2011

  • Liu, Lianchi; Bai, Chen; Sun, Huai
  • The Journal of Physical Chemistry A, Vol. 115, Issue 19
  • DOI: 10.1021/jp110435p

Early maturation processes in coal. Part 2: Reactive dynamics simulations using the ReaxFF reactive force field on Morwell Brown coal structures
journal, December 2009


Simulations on the Thermal Decomposition of a Poly(dimethylsiloxane) Polymer Using the ReaxFF Reactive Force Field
journal, May 2005

  • Chenoweth, Kimberly; Cheung, Sam; van Duin, Adri C. T.
  • Journal of the American Chemical Society, Vol. 127, Issue 19
  • DOI: 10.1021/ja050980t

Development and Validation of ReaxFF Reactive Force Field for Hydrocarbon Chemistry Catalyzed by Nickel
journal, February 2010

  • Mueller, Jonathan E.; van Duin, Adri C. T.; Goddard, William A.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 11
  • DOI: 10.1021/jp9035056

ReaxFF Reactive Force Field for Molecular Dynamics Simulations of Hydrocarbon Oxidation
journal, February 2008

  • Chenoweth, Kimberly; van Duin, Adri C. T.; Goddard, William A.
  • The Journal of Physical Chemistry A, Vol. 112, Issue 5
  • DOI: 10.1021/jp709896w

Geochemical Evolution of Occluded Hydrocarbons inside Geomacromolecules: A Review
journal, August 2017


Study of physical and chemical properties of vitrinites. Inferences on depositional and coalification controls
journal, September 1998


The temperatures of oil and gas formation in the sub-surface
journal, June 1988

  • Quigley, T. M.; Mackenzie, A. S.
  • Nature, Vol. 333, Issue 6173
  • DOI: 10.1038/333549a0

A Simple Kinetic Model of Oil Generation, Vaporization, Coking, and Cracking
journal, October 2015


State of the art of research in kinetic modelling of oil formation and expulsion
journal, January 1990


Simple kinetic models of petroleum formation. Part I: oil and gas generation from kerogen
journal, January 1995


On the mechanism of kerogen pyrolysis
journal, October 1984


Organic sulphur in macromolecular sedimentary organic matter: I. Structure and origin of sulphur-containing moieties in kerogen, asphaltenes and coal as revealed by flash pyrolysis
journal, April 1989

  • Sinninghe Damsté, Jaap S.; Eglinton, Timothy I.; De Leeuw, Jan W.
  • Geochimica et Cosmochimica Acta, Vol. 53, Issue 4
  • DOI: 10.1016/0016-7037(89)90032-X

Characterisation and differentiation of kerogens by pyrolytic and chemical degradation techniques
journal, April 2001

  • González-Vila, F. J.; Amblès, A.; del Rı́o, J. C.
  • Journal of Analytical and Applied Pyrolysis, Vol. 58-59
  • DOI: 10.1016/S0165-2370(00)00196-0

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


Parallel reactive molecular dynamics: Numerical methods and algorithmic techniques
journal, April 2012


Bond Dissociation Energies of Organic Molecules
journal, April 2003

  • Blanksby, Stephen J.; Ellison, G. Barney
  • Accounts of Chemical Research, Vol. 36, Issue 4
  • DOI: 10.1021/ar020230d

Bond Dissociation Energies by Kinetic Methods
journal, October 1966


New ideas of coal organic matter chemical structure and mechanism of hydrogenation processes
journal, July 1990


Reactions of methylene and ether bridges
journal, May 1984


Structural investigations of sulphur-rich macromolecular oil fractions and a kerogen by sequential chemical degradation
journal, December 1992


3D chemical model for geological macromolecules
journal, January 1990


ESR assessment of kerogen maturation and its relation with petroleum genesis
journal, January 1990


Kerogen Chemistry 6. Involvement of Native Free Radicals in Kerogen Thermal Deoxygenation
journal, September 2005

  • Larsen, John W.; Ashida, Ryuichi; Doetschman, David C.
  • Energy & Fuels, Vol. 19, Issue 5
  • DOI: 10.1021/ef0501288

Mechanisms of graphite formation from kerogen: experimental evidence
journal, October 1995


Molecular structure of organic components in cephalopods: Evidence for oxidative cross linking in fossil marine invertebrates
journal, October 2008


Statistical Mechanics of Cross‐Linked Polymer Networks I. Rubberlike Elasticity
journal, November 1943

  • Flory, Paul J.; Rehner, John
  • The Journal of Chemical Physics, Vol. 11, Issue 11
  • DOI: 10.1063/1.1723791

Critical experimental test of the Flory-Rehner theory of swelling
journal, October 1988

  • Neuburger, N. A.; Eichinger, B. E.
  • Macromolecules, Vol. 21, Issue 10
  • DOI: 10.1021/ma00188a026

Chemical reactions of polymer crosslinking and post-crosslinking at room and medium temperature
journal, February 2011


Development, applications and challenges of ReaxFF reactive force field in molecular simulations
journal, November 2015

  • Han, You; Jiang, Dandan; Zhang, Jinli
  • Frontiers of Chemical Science and Engineering, Vol. 10, Issue 1
  • DOI: 10.1007/s11705-015-1545-z

Thermal decomposition process in algaenan of Botryococcus braunii race L. Part 2: Molecular dynamics simulations using the ReaxFF reactive force field
journal, March 2009


Study of coal hydropyrolysis and desulfurization by ReaxFF molecular dynamics simulation
journal, April 2015


Large-Scale Reactive Molecular Dynamics Simulation and Kinetic Modeling of High-Temperature Pyrolysis of the Gloeocapsomorphaprisca Microfossils
journal, May 2014

  • Zou, Chenyu; Raman, Sumathy; van Duin, Adri C. T.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 23
  • DOI: 10.1021/jp501925a

Comparison of ReaxFF, DFTB, and DFT for Phenolic Pyrolysis. 2. Elementary Reaction Paths
journal, October 2013

  • Bauschlicher, Charles W.; Qi, Tingting; Reed, Evan J.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 44
  • DOI: 10.1021/jp408113w

The light hydrocarbons in petroleum: a critical review
journal, April 1997


Some Predicted Effects of Minerals on the Generation of Petroleum in Nature
journal, July 2016


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    Timescale prediction of complex multi-barrier pathways using flux sampling molecular dynamics and 1D kinetic integration: Application to cellulose dehydration
    journal, January 2020

    • Valdenaire, Pierre-Louis; Pellenq, Roland J. M.; Ulm, Franz J.
    • The Journal of Chemical Physics, Vol. 152, Issue 2
    • DOI: 10.1063/1.5126391

    Multi-scale evaluation of mechanical properties of the Bakken shale
    journal, September 2018

    • Li, Chunxiao; Ostadhassan, Mehdi; Abarghani, Arash
    • Journal of Materials Science, Vol. 54, Issue 3
    • DOI: 10.1007/s10853-018-2946-4