Catalytic deoxygenation of vapors obtained from ablative fast pyrolysis of wheat straw using mesoporous HZSM-5

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Abstract

Steam treated HZSM-5 with different Si/Al ratios were tested as catalysts for the upgrading of wheat straw pyrolysis vapors and their performance was compared to hierarchical counterparts, which were prepared by desilication followed by acid washing. Pyrolysis vapors were generated in an ablative system, hot gas filtered, and upgraded in an ex-situ catalyst bed to remove oxygen functionalities and reduce the oils' total acid number (TAN). Besides elemental analysis and TAN, the collected liquids were analyzed for water, chemical composition by gas chromatography mass spectrometry with flame ionization detection (GC–MS/FID), size exclusion chromatography (SEC), thermogravimetric analysis (TGA), and selectively by 1H nuclear magnetic resonance (NMR), 13C NMR, and two-dimensional heteronuclear single-quantum correlation (2D HSQC) NMR. Hierarchical and conventional catalysts were analyzed with X-ray fluorescence (XRF), ammonia temperature-programmed desorption (NH3-TPD) and ethylamine TPD, N2 and Ar-physisorption, transmission electron microscopy (TEM) and X-ray diffraction (XRD) to investigate changes induced by the desilication process. In addition, samples were analyzed after several reaction and regeneration cycles to investigate catalyst stability. The hierarchical samples showed an increased coking propensity compared to their parent version. The introduction of mesopores after desilication of HZSM-5 with molar Si/Al ratios of 29 and 39 lead to prolonged activity in deoxygenation and improved carbon recovery in the collected oil fractions compared to the parent counterparts. The results indicate that mild deoxygenation may be a viable way of pretreating pyrolysis oil before co-processing with fossil oil in refineries.
Original languageEnglish
Article number106119
JournalFuel Processing Technology
Volume194
Number of pages15
ISSN0378-3820
DOIs
Publication statusPublished - 2019

Keywords

  • Zeolites
  • Biomass
  • Heterogeneous catalysis
  • Desilication
  • Fast pyrolysis

Cite this

@article{e52a272d59a94eb9b2d8b5e9f801e849,
title = "Catalytic deoxygenation of vapors obtained from ablative fast pyrolysis of wheat straw using mesoporous HZSM-5",
abstract = "Steam treated HZSM-5 with different Si/Al ratios were tested as catalysts for the upgrading of wheat straw pyrolysis vapors and their performance was compared to hierarchical counterparts, which were prepared by desilication followed by acid washing. Pyrolysis vapors were generated in an ablative system, hot gas filtered, and upgraded in an ex-situ catalyst bed to remove oxygen functionalities and reduce the oils' total acid number (TAN). Besides elemental analysis and TAN, the collected liquids were analyzed for water, chemical composition by gas chromatography mass spectrometry with flame ionization detection (GC–MS/FID), size exclusion chromatography (SEC), thermogravimetric analysis (TGA), and selectively by 1H nuclear magnetic resonance (NMR), 13C NMR, and two-dimensional heteronuclear single-quantum correlation (2D HSQC) NMR. Hierarchical and conventional catalysts were analyzed with X-ray fluorescence (XRF), ammonia temperature-programmed desorption (NH3-TPD) and ethylamine TPD, N2 and Ar-physisorption, transmission electron microscopy (TEM) and X-ray diffraction (XRD) to investigate changes induced by the desilication process. In addition, samples were analyzed after several reaction and regeneration cycles to investigate catalyst stability. The hierarchical samples showed an increased coking propensity compared to their parent version. The introduction of mesopores after desilication of HZSM-5 with molar Si/Al ratios of 29 and 39 lead to prolonged activity in deoxygenation and improved carbon recovery in the collected oil fractions compared to the parent counterparts. The results indicate that mild deoxygenation may be a viable way of pretreating pyrolysis oil before co-processing with fossil oil in refineries.",
keywords = "Zeolites, Biomass, Heterogeneous catalysis, Desilication, Fast pyrolysis",
author = "Andreas Eschenbacher and Jensen, {Peter Arendt} and Henriksen, {Ulrik Birk} and Jesper Ahrenfeldt and Sokol Ndoni and Chengxin Li and Duus, {Jens {\O}llgaard} and Mentzel, {Uffe Vie} and Jensen, {Anker Degn}",
year = "2019",
doi = "10.1016/j.fuproc.2019.106119",
language = "English",
volume = "194",
journal = "Fuel Processing Technology",
issn = "0378-3820",
publisher = "Elsevier",

}

TY - JOUR

T1 - Catalytic deoxygenation of vapors obtained from ablative fast pyrolysis of wheat straw using mesoporous HZSM-5

AU - Eschenbacher, Andreas

AU - Jensen, Peter Arendt

AU - Henriksen, Ulrik Birk

AU - Ahrenfeldt, Jesper

AU - Ndoni, Sokol

AU - Li, Chengxin

AU - Duus, Jens Øllgaard

AU - Mentzel, Uffe Vie

AU - Jensen, Anker Degn

PY - 2019

Y1 - 2019

N2 - Steam treated HZSM-5 with different Si/Al ratios were tested as catalysts for the upgrading of wheat straw pyrolysis vapors and their performance was compared to hierarchical counterparts, which were prepared by desilication followed by acid washing. Pyrolysis vapors were generated in an ablative system, hot gas filtered, and upgraded in an ex-situ catalyst bed to remove oxygen functionalities and reduce the oils' total acid number (TAN). Besides elemental analysis and TAN, the collected liquids were analyzed for water, chemical composition by gas chromatography mass spectrometry with flame ionization detection (GC–MS/FID), size exclusion chromatography (SEC), thermogravimetric analysis (TGA), and selectively by 1H nuclear magnetic resonance (NMR), 13C NMR, and two-dimensional heteronuclear single-quantum correlation (2D HSQC) NMR. Hierarchical and conventional catalysts were analyzed with X-ray fluorescence (XRF), ammonia temperature-programmed desorption (NH3-TPD) and ethylamine TPD, N2 and Ar-physisorption, transmission electron microscopy (TEM) and X-ray diffraction (XRD) to investigate changes induced by the desilication process. In addition, samples were analyzed after several reaction and regeneration cycles to investigate catalyst stability. The hierarchical samples showed an increased coking propensity compared to their parent version. The introduction of mesopores after desilication of HZSM-5 with molar Si/Al ratios of 29 and 39 lead to prolonged activity in deoxygenation and improved carbon recovery in the collected oil fractions compared to the parent counterparts. The results indicate that mild deoxygenation may be a viable way of pretreating pyrolysis oil before co-processing with fossil oil in refineries.

AB - Steam treated HZSM-5 with different Si/Al ratios were tested as catalysts for the upgrading of wheat straw pyrolysis vapors and their performance was compared to hierarchical counterparts, which were prepared by desilication followed by acid washing. Pyrolysis vapors were generated in an ablative system, hot gas filtered, and upgraded in an ex-situ catalyst bed to remove oxygen functionalities and reduce the oils' total acid number (TAN). Besides elemental analysis and TAN, the collected liquids were analyzed for water, chemical composition by gas chromatography mass spectrometry with flame ionization detection (GC–MS/FID), size exclusion chromatography (SEC), thermogravimetric analysis (TGA), and selectively by 1H nuclear magnetic resonance (NMR), 13C NMR, and two-dimensional heteronuclear single-quantum correlation (2D HSQC) NMR. Hierarchical and conventional catalysts were analyzed with X-ray fluorescence (XRF), ammonia temperature-programmed desorption (NH3-TPD) and ethylamine TPD, N2 and Ar-physisorption, transmission electron microscopy (TEM) and X-ray diffraction (XRD) to investigate changes induced by the desilication process. In addition, samples were analyzed after several reaction and regeneration cycles to investigate catalyst stability. The hierarchical samples showed an increased coking propensity compared to their parent version. The introduction of mesopores after desilication of HZSM-5 with molar Si/Al ratios of 29 and 39 lead to prolonged activity in deoxygenation and improved carbon recovery in the collected oil fractions compared to the parent counterparts. The results indicate that mild deoxygenation may be a viable way of pretreating pyrolysis oil before co-processing with fossil oil in refineries.

KW - Zeolites

KW - Biomass

KW - Heterogeneous catalysis

KW - Desilication

KW - Fast pyrolysis

U2 - 10.1016/j.fuproc.2019.106119

DO - 10.1016/j.fuproc.2019.106119

M3 - Journal article

VL - 194

JO - Fuel Processing Technology

JF - Fuel Processing Technology

SN - 0378-3820

M1 - 106119

ER -