Across-Phase Biomass Pyrolysis Stoichiometry, Energy Balance, and Product Formation Kinetics

Jeffrey Leblanc; Minori Uchimiya; Girish Ramakrishnan; Marco J. Castaldi; Alexander Orlov

doi:10.1021/acs.energyfuels.6b01376

Across-Phase Biomass Pyrolysis Stoichiometry, Energy Balance, and Product Formation Kinetics

Jeffrey Leblanc
, Minori Uchimiya
, Girish Ramakrishnan
, Marco J. Castaldi
, Alexander Orlov

Materials Science and Engineering

City University of New York
Stony Brook University
United States Department of Agriculture

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

Abstract

Predictive correlations between reactions occurring in the gas, liquid, and solid phases are necessary to economically utilize the thermochemical conversion of agricultural wastes impacting the food, water, and energy nexus. On the basis of an empirical mass balance (99.7%), this study established the overall reaction stoichiometry (C_33.42H_45.95O_20.26N_0.22S_0.14 = 0.50C_20.08H_57.21O_22.46N_0.20S_0.22 + 1.72H₂O + 0.10H₂ + 1.07CH₄ + 0.02C₂H₄ + 0.06C₂H₆ + 2.21CO₂ + 2.05CO + 0.28C_63.75H_32.47O_3.23N_0.43S_0.12) and energy balance for the slow pyrolysis of lignocellulosic pecan shell waste biomass at 10 °C min^-1 up to 500 °C. In situ thermogravimetry-gas chromatography and diffuse reflectance infrared fourier transform spectroscopy (DRIFTs) were used to link the gas-, liquid-, and solid-phase nonisothermal reaction kinetics. Gaussian fit-based deconvolution of individual gaseous product formation rates (hydrogen, methane, carbon monoxide, carbon dioxide, ethylene, and ethane in mg min^-1) suggested the relationships between (1) evolved methane and increased aromaticity/energy density of char product at 300-500 °C, and (2) evolved carbon dioxide and decarboxylation of char product near 400 °C. Partial least-squares (PLS) calibrations were obtained between (1) DRIFTs monitoring of the surface functional groups in the solid phase (transition from pecan shell to char) and (2) CO, CO₂, CH₄, C₂H₆, C₂H₄, and tar formation profiles in the gas/condensable phase. Established across-phase PLS calibrations can be used to predict biochar's surface chemistry based on the fingerprint of volatile products, and vice versa. These new thermodynamic (reaction stoichiometry and energy balance) and kinetic (deconvolution of specific gas formation rates and PLS) predictive methodologies will facilitate the nexus of food, water (designing of biochar soil amendment), and energy (optimization of syngas and bio-oil composition) enabling sustainable agriculture.

Original language	English
Pages (from-to)	6537-6546
Number of pages	10
Journal	Energy and Fuels
Volume	30
Issue number	8
DOIs	https://doi.org/10.1021/acs.energyfuels.6b01376
State	Published - Aug 18 2016

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@article{448a135e088e42d78e8861c1c7f125a9,

title = "Across-Phase Biomass Pyrolysis Stoichiometry, Energy Balance, and Product Formation Kinetics",

abstract = "Predictive correlations between reactions occurring in the gas, liquid, and solid phases are necessary to economically utilize the thermochemical conversion of agricultural wastes impacting the food, water, and energy nexus. On the basis of an empirical mass balance (99.7\%), this study established the overall reaction stoichiometry (C33.42H45.95O20.26N0.22S0.14 = 0.50C20.08H57.21O22.46N0.20S0.22 + 1.72H2O + 0.10H2 + 1.07CH4 + 0.02C2H4 + 0.06C2H6 + 2.21CO2 + 2.05CO + 0.28C63.75H32.47O3.23N0.43S0.12) and energy balance for the slow pyrolysis of lignocellulosic pecan shell waste biomass at 10 °C min-1 up to 500 °C. In situ thermogravimetry-gas chromatography and diffuse reflectance infrared fourier transform spectroscopy (DRIFTs) were used to link the gas-, liquid-, and solid-phase nonisothermal reaction kinetics. Gaussian fit-based deconvolution of individual gaseous product formation rates (hydrogen, methane, carbon monoxide, carbon dioxide, ethylene, and ethane in mg min-1) suggested the relationships between (1) evolved methane and increased aromaticity/energy density of char product at 300-500 °C, and (2) evolved carbon dioxide and decarboxylation of char product near 400 °C. Partial least-squares (PLS) calibrations were obtained between (1) DRIFTs monitoring of the surface functional groups in the solid phase (transition from pecan shell to char) and (2) CO, CO2, CH4, C2H6, C2H4, and tar formation profiles in the gas/condensable phase. Established across-phase PLS calibrations can be used to predict biochar's surface chemistry based on the fingerprint of volatile products, and vice versa. These new thermodynamic (reaction stoichiometry and energy balance) and kinetic (deconvolution of specific gas formation rates and PLS) predictive methodologies will facilitate the nexus of food, water (designing of biochar soil amendment), and energy (optimization of syngas and bio-oil composition) enabling sustainable agriculture.",

author = "Jeffrey Leblanc and Minori Uchimiya and Girish Ramakrishnan and Castaldi, \{Marco J.\} and Alexander Orlov",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = aug,

day = "18",

doi = "10.1021/acs.energyfuels.6b01376",

language = "English",

volume = "30",

pages = "6537--6546",

journal = "Energy and Fuels",

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T1 - Across-Phase Biomass Pyrolysis Stoichiometry, Energy Balance, and Product Formation Kinetics

AU - Leblanc, Jeffrey

AU - Uchimiya, Minori

AU - Ramakrishnan, Girish

AU - Castaldi, Marco J.

AU - Orlov, Alexander

PY - 2016/8/18

Y1 - 2016/8/18

N2 - Predictive correlations between reactions occurring in the gas, liquid, and solid phases are necessary to economically utilize the thermochemical conversion of agricultural wastes impacting the food, water, and energy nexus. On the basis of an empirical mass balance (99.7%), this study established the overall reaction stoichiometry (C33.42H45.95O20.26N0.22S0.14 = 0.50C20.08H57.21O22.46N0.20S0.22 + 1.72H2O + 0.10H2 + 1.07CH4 + 0.02C2H4 + 0.06C2H6 + 2.21CO2 + 2.05CO + 0.28C63.75H32.47O3.23N0.43S0.12) and energy balance for the slow pyrolysis of lignocellulosic pecan shell waste biomass at 10 °C min-1 up to 500 °C. In situ thermogravimetry-gas chromatography and diffuse reflectance infrared fourier transform spectroscopy (DRIFTs) were used to link the gas-, liquid-, and solid-phase nonisothermal reaction kinetics. Gaussian fit-based deconvolution of individual gaseous product formation rates (hydrogen, methane, carbon monoxide, carbon dioxide, ethylene, and ethane in mg min-1) suggested the relationships between (1) evolved methane and increased aromaticity/energy density of char product at 300-500 °C, and (2) evolved carbon dioxide and decarboxylation of char product near 400 °C. Partial least-squares (PLS) calibrations were obtained between (1) DRIFTs monitoring of the surface functional groups in the solid phase (transition from pecan shell to char) and (2) CO, CO2, CH4, C2H6, C2H4, and tar formation profiles in the gas/condensable phase. Established across-phase PLS calibrations can be used to predict biochar's surface chemistry based on the fingerprint of volatile products, and vice versa. These new thermodynamic (reaction stoichiometry and energy balance) and kinetic (deconvolution of specific gas formation rates and PLS) predictive methodologies will facilitate the nexus of food, water (designing of biochar soil amendment), and energy (optimization of syngas and bio-oil composition) enabling sustainable agriculture.

AB - Predictive correlations between reactions occurring in the gas, liquid, and solid phases are necessary to economically utilize the thermochemical conversion of agricultural wastes impacting the food, water, and energy nexus. On the basis of an empirical mass balance (99.7%), this study established the overall reaction stoichiometry (C33.42H45.95O20.26N0.22S0.14 = 0.50C20.08H57.21O22.46N0.20S0.22 + 1.72H2O + 0.10H2 + 1.07CH4 + 0.02C2H4 + 0.06C2H6 + 2.21CO2 + 2.05CO + 0.28C63.75H32.47O3.23N0.43S0.12) and energy balance for the slow pyrolysis of lignocellulosic pecan shell waste biomass at 10 °C min-1 up to 500 °C. In situ thermogravimetry-gas chromatography and diffuse reflectance infrared fourier transform spectroscopy (DRIFTs) were used to link the gas-, liquid-, and solid-phase nonisothermal reaction kinetics. Gaussian fit-based deconvolution of individual gaseous product formation rates (hydrogen, methane, carbon monoxide, carbon dioxide, ethylene, and ethane in mg min-1) suggested the relationships between (1) evolved methane and increased aromaticity/energy density of char product at 300-500 °C, and (2) evolved carbon dioxide and decarboxylation of char product near 400 °C. Partial least-squares (PLS) calibrations were obtained between (1) DRIFTs monitoring of the surface functional groups in the solid phase (transition from pecan shell to char) and (2) CO, CO2, CH4, C2H6, C2H4, and tar formation profiles in the gas/condensable phase. Established across-phase PLS calibrations can be used to predict biochar's surface chemistry based on the fingerprint of volatile products, and vice versa. These new thermodynamic (reaction stoichiometry and energy balance) and kinetic (deconvolution of specific gas formation rates and PLS) predictive methodologies will facilitate the nexus of food, water (designing of biochar soil amendment), and energy (optimization of syngas and bio-oil composition) enabling sustainable agriculture.

UR - https://www.scopus.com/pages/publications/84983616762

U2 - 10.1021/acs.energyfuels.6b01376

DO - 10.1021/acs.energyfuels.6b01376

M3 - Article

AN - SCOPUS:84983616762

SN - 0887-0624

VL - 30

SP - 6537

EP - 6546

JO - Energy and Fuels

JF - Energy and Fuels

IS - 8

ER -

Across-Phase Biomass Pyrolysis Stoichiometry, Energy Balance, and Product Formation Kinetics

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