Large-scale atomistic model construction of subbituminous and bituminous coals for solvent extraction simulations with reactive molecular dynamics

Pilsun Yoo, Gang Seob Jung, Matthew R. Ryder, Frederic Vautard, Ercan Cakmak, Sungsool Wi, Matthew C. Weisenberger, Edgar Lara-Curzio, Jonathan P. Mathews, Stephan Irle

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

Large-scale atomistic models for complex polycyclic aromatic hydrocarbon systems help understand the chemical properties and behaviors of complex feedstocks such as coal or petroleum. However, the development and utilization of large-scale models remain limited due to the difficulty in achieving the varied structural characteristics necessary to capture stochastic nature of these feedstocks. We demonstrate a systematic workflow to construct stochastic molecular systems from a broad analytical suite: high-resolution transmission electron microscopy (HRTEM), carbon-13 nuclear magnetic resonance spectroscopy (13C NMR), laser desorption ionization mass spectroscopy (LDI-MS), and elemental analysis. We present a model construction and analysis utility of a new Python-based module. We selected one subbituminous and three high-volatile bituminous coals to construct large-scale models (∼40,000 atoms). The constructed models were utilized to examine the affinity for solvent extraction (naphthalene or tetralin) and the effect of structural properties (e.g., aromatic cluster size, functional groups, and cross-linking) in reactive molecular dynamics simulations. Complex chemical reactions were monitored with bond order transitions, intermediates formation, and mass distributions. Reactive molecular dynamics simulations suggest a plausible chemical extraction process and products for the complex fossil feedstocks. The results indicated that radical formations with bond breaking of bridging oxygens and carbons were required at high temperatures to facilitate hydrogeneration and extraction of gas molecules from radical-free molecules. We observed that aliphatic chains of tetralin were easily decomposed and combined with radicals to form small size of molecules with aryl bonding, mainly increasing molecules in the 500–1000 Da, while naphthalene had little impact on chemical extraction process.

Original languageEnglish
Article number118939
JournalCarbon
Volume222
DOIs
StatePublished - Mar 25 2024

Funding

NOTICE OF COPYRIGHT: This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan).This research work was sponsored by the U.S. Department of Energy Fossil Energy and Carbon Management Program, Advanced Coal Processing Program, C4WARD project (FEAA155). This research used the resources of the Compute and Data Environment for Science (CADES) at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725. A portion of this work was performed at the National High Magnetic Field Laboratory NMR User Facility, which is supported by the National Science Foundation Division of Chemistry and Division of Materials Research through DMR-2128556 and the State of Florida. The authors also acknowledge the University of Kentucky Center for Applied Energy Research analytical group for the proximate and ultimate analyses of the coals. This research work was sponsored by the U.S. Department of Energy Fossil Energy and Carbon Management Program, Advanced Coal Processing Program, C4WARD project (FEAA155). This research used the resources of the Compute and Data Environment for Science (CADES) at the Oak Ridge National Laboratory , which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725. A portion of this work was performed at the National High Magnetic Field Laboratory NMR User Facility, which is supported by the National Science Foundation Division of Chemistry and Division of Materials Research through DMR-2128556 and the State of Florida. The authors also acknowledge the University of Kentucky Center for Applied Energy Research analytical group for the proximate and ultimate analyses of the coals. NOTICE OF COPYRIGHT: This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ).

Keywords

  • Atomistic coal model
  • Bottom-up carbonaceous model construction
  • Ensemble of macromolecules
  • Reactive molecular dynamics simulations of coal
  • Solvent extraction

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