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Behaviors and non-isothermal kinetics of Chlorella pyrenoidosa fodder pyrolysis by a modified kinetic compensation effects and a parallel two-step reaction model

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Abstract

The TG-FTIR and Py-GC/MS techniques are applied to investigate the behaviors and kinetics of the Chlorella pyrenoidosa fodder (CPF) pyrolysis under slow and fast heating, respectively. TG-FTIR results reveal that the CPF pyrolysis mainly occurs in temperature range of 150–600 ℃, where 432 ℃ is responsible for the fastest releases of bio-oil and gases. The NH3 and nitrogenous organic compounds derived from protein decomposition generate over the entire pyrolytic temperature range. According to the Py-GC/MS, the bio-oil has maximum contents of C11-C22 (~ 66.5 wt%) and C4-C10 (~ 99.2%) compounds at 600℃ and 800℃, respectively. Higher pyrolytic temperature is appropriate for bio-oil conversion to gasoline energy potential. Temperature increasing can convert the C11-C22 into C4-C10, attributing to cracking the long carbon chain to a shorter length. The Vyazovkin method and a modified kinetic compensation effects (KCE) model are adopted in model-free procedure to investigate the single-step pyrolysis of CPF. Kinetic results showed that the CPF pyrolysis has an average activation energy of 181.7 kJ/mol. But the activation energy varies greatly with conversion rate from 128 kJ/mol to 438 kJ/mol attributing to mechanism changes. The modified KCE model, which enabled activation energy fluctuations, could optimize the single-step pyrolysis of CPF with reaction order of n = 7.8. A parallel two-step reaction (PTSR) model which assumes the pseudo protein and carbohydrate decompose independently in two-step reaction was developed to depict the multi-step pyrolysis of CPF. This PTSR model could fit the experiments well with very low relative deviation. The activation energies of pseudo protein and carbohydrate were 94.22 kJ/mol and 154.85 kJ/mol in the first-step reaction and 109.37 kJ/mol and 142.84 kJ/mol in the first and second step reaction, respectively. The lipid pyrolysis follows a single-step reaction with activation energy of 156.83 kJ/mol.

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Data availability

Some or all data, models, or code that support the findings of this study are available from the corresponding author upon reasonable request.

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Funding

Authors would like to acknowledge the funding from Key Scientific Research Project of Henan Province (No.21A610006), Youth Science Foundation of Henan Normal University (No.5101219170815), and analysis technical supports from Instrumental Analysis & Research Center of Sun Yat-Sen University.

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Authors and Affiliations

  1. School of Environment, International Joint Laboratory On Key Techniques in Water Treatment, Henan Normal University, Xinxiang, 453007, Henan Province, China

    Xiaoxuan Wang, Yanxue Wang, Jiaru Guo, Yali Zhao, Xin Zhang & Zhihua Chen

  2. School of Environmental Science & Engineering, Huazhong University of Science & Technology, Wuhan, 430074, China

    Xun Wang

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  1. Xiaoxuan Wang
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Contributions

Xiaoxuan Wang contributed to visualization, data curation, investigation, and data curation; Yanxue Wang contributed to data curation and investigation; Jiaru Guo contributed to formal analysis and validation; Yali Zhao contributed to formal analysis and validation; Xun Wang contributed to software; Xin Zhang contributed to writing—review and editing, supervision, funding acquisition, and project administration; Zhihua Chen contributed to writing—original draft, validation, methodology, and conceptualization.

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Correspondence to Zhihua Chen.

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Wang, X., Wang, Y., Guo, J. et al. Behaviors and non-isothermal kinetics of Chlorella pyrenoidosa fodder pyrolysis by a modified kinetic compensation effects and a parallel two-step reaction model. Biomass Conv. Bioref. 14, 5589–5600 (2024). https://doi.org/10.1007/s13399-022-02723-7

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