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Effects of demineralization on the composition of microalgae pyrolysis volatiles in py-GC–MS

Qi Niu (UGent) , Stef Ghysels (UGent) , Nannan Wu (UGent) , Diederik Rousseau (UGent) , Jan Pieters (UGent) , Wolter Prins (UGent) and Frederik Ronsse (UGent)
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Abstract
This study compared the volatiles distribution in analytical scale pyrolysis (py-GC-MS) of Nannochloropsis gaditana (marine microalgae) and Scenedesmus almeriensis (freshwater microalgae) and their demineralized counterparts. The role of inorganic elements and their removal via ultrasonic treatment, water washing and (in) organic acid leaching were elucidated. Principal component analysis (PCA) and grey relational analysis were applied to analyze the pyrolysis volatiles distribution and demonstrate the influence of inorganic elements in pyrolysis, respectively. Demineralization affects (breaks down) the chemical structure of carbohydrates, followed by (to a lesser extent) proteins and lipids. Acid leaching promoted hydrolysis and suppressed the catalytic effect associated to inorganic elements in subsequent pyrolysis, compared to ultrasonic treatment and water washing. Elements like K and Na had a larger catalytic influence on microalgae pyrolysis than Ca and Mg. The composition and pyrolytic formation mechanism of major product groups at 500 degrees C were studied, including anhydrosugars, phenolics, furans, carboxylic acids, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, N-heterocyclic compounds, nitriles and amides. The results indicate that demineralization shows positive effects on fast pyrolysis of microalgae: (1) by disrupting the cell wall and releasing the lipids and cellular contents. Based on the py-GC-MS peak area normalized to sample mass, the relative contribution of hydrocarbons in the pyrolysis vapors increased from 25.5 % (NG: Nannochloropsis gaditana) to 32.1 % (NG-HCl: Nannochloropsis gaditana, HCl treated), and from 16.1 % (SA: Scenedesmus almeriensis) to 22.4 % (SA-HCl: Scenedesmus almeriensis, HCl treated); (2) by decreasing the relative yields in O-containing compounds resulting from the suppressed catalytic effects of alkali and alkaline earth metals (53.3 % (NG) to 37.1 % (NG-HCl), 57.5 % (SA) to 47.8 % (SA-HCl)) that would otherwise have been present in non-demineralized microalgae feedstock. The effects of demineralization on the denitrogenation of pyrolysis vapors were not that obvious. Suggestions for potential full scale applications have been proposed.
Keywords
Energy Engineering and Power Technology, Fuel Technology, Nuclear Energy and Engineering, Renewable Energy, Sustainability and the Environment, Microalgae, Fast pyrolysis, Inorganic elements, Demineralization, Deoxygenation, CATALYTIC FAST PYROLYSIS, BIO-OIL, THERMAL-DEGRADATION, ALGAE PYROLYSIS, BIOMASS, PRETREATMENT, CONVERSION, MECHANISM, QUALITY, CARBOHYDRATE

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MLA
Niu, Qi, et al. “Effects of Demineralization on the Composition of Microalgae Pyrolysis Volatiles in Py-GC–MS.” ENERGY CONVERSION AND MANAGEMENT, vol. 251, 2022, doi:10.1016/j.enconman.2021.114979.
APA
Niu, Q., Ghysels, S., Wu, N., Rousseau, D., Pieters, J., Prins, W., & Ronsse, F. (2022). Effects of demineralization on the composition of microalgae pyrolysis volatiles in py-GC–MS. ENERGY CONVERSION AND MANAGEMENT, 251. https://doi.org/10.1016/j.enconman.2021.114979
Chicago author-date
Niu, Qi, Stef Ghysels, Nannan Wu, Diederik Rousseau, Jan Pieters, Wolter Prins, and Frederik Ronsse. 2022. “Effects of Demineralization on the Composition of Microalgae Pyrolysis Volatiles in Py-GC–MS.” ENERGY CONVERSION AND MANAGEMENT 251. https://doi.org/10.1016/j.enconman.2021.114979.
Chicago author-date (all authors)
Niu, Qi, Stef Ghysels, Nannan Wu, Diederik Rousseau, Jan Pieters, Wolter Prins, and Frederik Ronsse. 2022. “Effects of Demineralization on the Composition of Microalgae Pyrolysis Volatiles in Py-GC–MS.” ENERGY CONVERSION AND MANAGEMENT 251. doi:10.1016/j.enconman.2021.114979.
Vancouver
1.
Niu Q, Ghysels S, Wu N, Rousseau D, Pieters J, Prins W, et al. Effects of demineralization on the composition of microalgae pyrolysis volatiles in py-GC–MS. ENERGY CONVERSION AND MANAGEMENT. 2022;251.
IEEE
[1]
Q. Niu et al., “Effects of demineralization on the composition of microalgae pyrolysis volatiles in py-GC–MS,” ENERGY CONVERSION AND MANAGEMENT, vol. 251, 2022.
@article{8727277,
  abstract     = {{This study compared the volatiles distribution in analytical scale pyrolysis (py-GC-MS) of Nannochloropsis gaditana (marine microalgae) and Scenedesmus almeriensis (freshwater microalgae) and their demineralized counterparts. The role of inorganic elements and their removal via ultrasonic treatment, water washing and (in) organic acid leaching were elucidated. Principal component analysis (PCA) and grey relational analysis were applied to analyze the pyrolysis volatiles distribution and demonstrate the influence of inorganic elements in pyrolysis, respectively. Demineralization affects (breaks down) the chemical structure of carbohydrates, followed by (to a lesser extent) proteins and lipids. Acid leaching promoted hydrolysis and suppressed the catalytic effect associated to inorganic elements in subsequent pyrolysis, compared to ultrasonic treatment and water washing. Elements like K and Na had a larger catalytic influence on microalgae pyrolysis than Ca and Mg. The composition and pyrolytic formation mechanism of major product groups at 500 degrees C were studied, including anhydrosugars, phenolics, furans, carboxylic acids, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, N-heterocyclic compounds, nitriles and amides. The results indicate that demineralization shows positive effects on fast pyrolysis of microalgae: (1) by disrupting the cell wall and releasing the lipids and cellular contents. Based on the py-GC-MS peak area normalized to sample mass, the relative contribution of hydrocarbons in the pyrolysis vapors increased from 25.5 % (NG: Nannochloropsis gaditana) to 32.1 % (NG-HCl: Nannochloropsis gaditana, HCl treated), and from 16.1 % (SA: Scenedesmus almeriensis) to 22.4 % (SA-HCl: Scenedesmus almeriensis, HCl treated); (2) by decreasing the relative yields in O-containing compounds resulting from the suppressed catalytic effects of alkali and alkaline earth metals (53.3 % (NG) to 37.1 % (NG-HCl), 57.5 % (SA) to 47.8 % (SA-HCl)) that would otherwise have been present in non-demineralized microalgae feedstock. The effects of demineralization on the denitrogenation of pyrolysis vapors were not that obvious. Suggestions for potential full scale applications have been proposed.}},
  articleno    = {{114979}},
  author       = {{Niu, Qi and Ghysels, Stef and Wu, Nannan and Rousseau, Diederik and Pieters, Jan and Prins, Wolter and Ronsse, Frederik}},
  issn         = {{0196-8904}},
  journal      = {{ENERGY CONVERSION AND MANAGEMENT}},
  keywords     = {{Energy Engineering and Power Technology,Fuel Technology,Nuclear Energy and Engineering,Renewable Energy,Sustainability and the Environment,Microalgae,Fast pyrolysis,Inorganic elements,Demineralization,Deoxygenation,CATALYTIC FAST PYROLYSIS,BIO-OIL,THERMAL-DEGRADATION,ALGAE PYROLYSIS,BIOMASS,PRETREATMENT,CONVERSION,MECHANISM,QUALITY,CARBOHYDRATE}},
  language     = {{eng}},
  pages        = {{14}},
  title        = {{Effects of demineralization on the composition of microalgae pyrolysis volatiles in py-GC–MS}},
  url          = {{http://doi.org/10.1016/j.enconman.2021.114979}},
  volume       = {{251}},
  year         = {{2022}},
}

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