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Quantum chemical investigation of the primary thermal pyrolysis reactions of the sodium carboxylate group in a brown coal model

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Abstract

The primary pyrolysis mechanisms of the sodium carboxylate group in sodium benzoate—used as a model compound of brown coal—were studied by performing quantum chemical computations using B3LYP and the CBS method. Various possible reaction pathways involving reactions such as unimolecular and bimolecular decarboxylation and decarbonylation, crosslinking, and radical attack in the brown coal matrix were explored. Without the participation of reactive radicals, unimolecular decarboxylation to release CO2 was calculated to be the most energetically favorable primary reaction pathway at the B3LYP/6-311+G (d, p) level of theory, and was also found to be more energetically favorable than decarboxylation of an carboxylic acid group. When CBS-QBS results were included, crosslinking between the sodium carboxylate group and the carboxylic acid and the decarboxylation of the sodium carboxylate group (catalyzed by the phenolic hydroxyl group) were found to be possible; this pathway competes with unimolecular decarboxylation of the sodium carboxylate group. Provided that H and CH3 radicals are present in the brown coal matrix and can access the sodium carboxylate group, accelerated pyrolysis of the sodium carboxylate group becomes feasible, leading to the release of an Na atom or an NaCO2 radical at the B3LYP/6-311+G (d, p) or CBS-QB3 level of theory, respectively.

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Acknowledgments

Financial support from the National Natural Science Foundation of China (no. 51404162) is gratefully acknowledged.

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Authors and Affiliations

  1. College of Mining Engineering, Taiyuan University of Technology, No.79 West Yingze Street, Taiyuan, Shanxi, 030024, People’s Republic of China

    Jian Li, Baisheng Zhang, Zhiqiang Zhang & Lixun Kang

  2. Key Laboratory of Renewable Energy and Gas Hydrate, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou, 510640, People’s Republic of China

    Kefeng Yan

  3. Guangzhou Center for Gas Hydrate Research, Chinese Academy of Sciences, Guangzhou, 510640, People’s Republic of China

    Kefeng Yan

Authors
  1. Jian Li
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  2. Baisheng Zhang
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  3. Zhiqiang Zhang
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  4. Kefeng Yan
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  5. Lixun Kang
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Correspondence to Zhiqiang Zhang.

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Li, J., Zhang, B., Zhang, Z. et al. Quantum chemical investigation of the primary thermal pyrolysis reactions of the sodium carboxylate group in a brown coal model. J Mol Model 20, 2523 (2014). https://doi.org/10.1007/s00894-014-2523-y

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