Macroscale properties and atomic-scale mechanisms of ash removal in low-temperature hydrothermal carbonization

Yu, Yan; Wan, Zhangmin; Smith, Micholas Dean; Mohan, Mood; Sokhansanj, Shahabaddine; Lau, Anthony; Smith, Jeremy C.; Rojas, Orlando J.

doi:10.1016/j.cej.2024.156913

Title: Macroscale properties and atomic-scale mechanisms of ash removal in low-temperature hydrothermal carbonization

Journal Article · 19 October 2024 · Chemical Engineering Journal

DOI: https://doi.org/10.1016/j.cej.2024.156913 · OSTI ID:2476606

^[1]; Wan, Zhangmin ^[2]; Smith, Micholas Dean ^[3];

^[1]; Sokhansanj, Shahabaddine ^[2];

^[2]; Smith, Jeremy C. ^[3];

^[2]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Univ. of British Columbia, Vancouver, BC (Canada)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

Biogenic ash is a significant impediment to the utilization of agricultural residues in biofuel production. Such challenge can be addressed by various treatments, as demonstrated in this study on the experimental and computational mechanisms involved in the hydrothermal treatment (HT) of wheat straw. A combination of classical (all-atom) molecular dynamics simulations of cellulose carrying silica and calcium species, along with first principles quantum chemical calculations, indicates the dissociation of inorganics from the cellulose with increased HT temperature. Here, this observation is confirmed by experimental evidence of effective ash removal by HT, showing at least 50% removal of sulfur, chlorine, potassium, and calcium, and 12.5% of silica, leading to a reduced total ash content (from 6.7% to 4.2%).Changes in structural features upon HT, such as surface cellular structure and porosity, were revealed, accompanied by an increased specific surface area (from 1.17 to 6.34 m²/g). Our simulations suggest that silica binds tightly to the hydrophobic face of cellulose at room temperature, but HT significantly reduces the binding free energy of association with both hydrophobic and hydrophilic surfaces. Most significantly, ash removal leads to an increased calorific value, rising from approximately 16 MJ/kg to about 19 MJ/kg, along with improved thermal behavior. The improved integration combustion index parameter S indicates that the combustion properties improve with ash removal efficiency. The proposed atomic-level mechanism for the observed removal of inorganics during mild HT underscores the potential of such treatment in producing energy-dense wheat straw, a widely available agricultural residue.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2476606

Journal Information:: Chemical Engineering Journal, Journal Name: Chemical Engineering Journal Vol. 500; ISSN 1385-8947

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Ash removal
Combustion kinetics
Free energy
Hydrothermal treatment
Molecular dynamics simulation
Wheat straw

Title: Macroscale properties and atomic-scale mechanisms of ash removal in low-temperature hydrothermal carbonization

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References (56)

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