Slow and fast pyrolysis of Douglas-fir lignin: Importance of liquid-intermediate formation on the distribution of products

Shuai Zhou, Brennan Pecha, Michiel van Kuppevelt, Armando G. McDonald, Manuel Garcia-Perez

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Abstract

The formation of liquid intermediates and the distribution of products were studied under slow and fast pyrolysis conditions. Results indicate that monomers are formed from lignin oligomeric products during secondary reactions, rather than directly from the native lignin. Lignin from Douglas-fir (Pseudotsuga menziesii) wood was extracted using the milled wood enzyme lignin isolation method. Slow pyrolysis using a microscope with hot-stage captured the liquid formation (>150 °C), shrinking, swelling (foaming), and evaporation behavior of lignin intermediates. The activation energy (Ea) for 5–80% conversions was 213 kJ mol−1, and the pre-exponential factor (log A) was 24.34. Fast pyrolysis tests in a wire mesh reactor were conducted (300–650 °C). The formation of the liquid intermediate was visualized with a fast speed camera (250 Hz), showing the existence of three well defined steps: formation of lignin liquid intermediates, foaming and liquid intermediate swelling, and evaporation and droplet shrinking. GC/MS and UV-Fluorescence of the mesh reactor condensate revealed lignin oligomer formation but no mono-phenols were seen. An increase in pyrolytic lignin yield was observed as temperature increased. The molar mass determined by ESI-MS was not affected by pyrolysis temperature. SEM of the char showed a smooth surface with holes, evidence of a liquid intermediate with foaming; bursting from these foams could be responsible for the removal of lignin oligomers. Py-GC/MS studies showed the highest yield of guaiacol compounds at 450–550 °C.
Original languageEnglish
Pages (from-to)398-409
JournalBiomass & bioenergy
Volume66
DOIs
Publication statusPublished - 2014

Fingerprint

pyrolysis
Lignin
Pseudotsuga menziesii
lignin
Pyrolysis
liquid
liquids
Liquids
foaming
Oligomers
swelling
Swelling
evaporation
Wood
Evaporation
distribution
product
guaiacol
Molar mass
isolation techniques

Keywords

  • IR-96746
  • METIS-311172

Cite this

Zhou, Shuai ; Pecha, Brennan ; van Kuppevelt, Michiel ; McDonald, Armando G. ; Garcia-Perez, Manuel. / Slow and fast pyrolysis of Douglas-fir lignin: Importance of liquid-intermediate formation on the distribution of products. In: Biomass & bioenergy. 2014 ; Vol. 66. pp. 398-409.
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abstract = "The formation of liquid intermediates and the distribution of products were studied under slow and fast pyrolysis conditions. Results indicate that monomers are formed from lignin oligomeric products during secondary reactions, rather than directly from the native lignin. Lignin from Douglas-fir (Pseudotsuga menziesii) wood was extracted using the milled wood enzyme lignin isolation method. Slow pyrolysis using a microscope with hot-stage captured the liquid formation (>150 °C), shrinking, swelling (foaming), and evaporation behavior of lignin intermediates. The activation energy (Ea) for 5–80{\%} conversions was 213 kJ mol−1, and the pre-exponential factor (log A) was 24.34. Fast pyrolysis tests in a wire mesh reactor were conducted (300–650 °C). The formation of the liquid intermediate was visualized with a fast speed camera (250 Hz), showing the existence of three well defined steps: formation of lignin liquid intermediates, foaming and liquid intermediate swelling, and evaporation and droplet shrinking. GC/MS and UV-Fluorescence of the mesh reactor condensate revealed lignin oligomer formation but no mono-phenols were seen. An increase in pyrolytic lignin yield was observed as temperature increased. The molar mass determined by ESI-MS was not affected by pyrolysis temperature. SEM of the char showed a smooth surface with holes, evidence of a liquid intermediate with foaming; bursting from these foams could be responsible for the removal of lignin oligomers. Py-GC/MS studies showed the highest yield of guaiacol compounds at 450–550 °C.",
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author = "Shuai Zhou and Brennan Pecha and {van Kuppevelt}, Michiel and McDonald, {Armando G.} and Manuel Garcia-Perez",
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Slow and fast pyrolysis of Douglas-fir lignin: Importance of liquid-intermediate formation on the distribution of products. / Zhou, Shuai; Pecha, Brennan; van Kuppevelt, Michiel; McDonald, Armando G.; Garcia-Perez, Manuel.

In: Biomass & bioenergy, Vol. 66, 2014, p. 398-409.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Slow and fast pyrolysis of Douglas-fir lignin: Importance of liquid-intermediate formation on the distribution of products

AU - Zhou, Shuai

AU - Pecha, Brennan

AU - van Kuppevelt, Michiel

AU - McDonald, Armando G.

AU - Garcia-Perez, Manuel

PY - 2014

Y1 - 2014

N2 - The formation of liquid intermediates and the distribution of products were studied under slow and fast pyrolysis conditions. Results indicate that monomers are formed from lignin oligomeric products during secondary reactions, rather than directly from the native lignin. Lignin from Douglas-fir (Pseudotsuga menziesii) wood was extracted using the milled wood enzyme lignin isolation method. Slow pyrolysis using a microscope with hot-stage captured the liquid formation (>150 °C), shrinking, swelling (foaming), and evaporation behavior of lignin intermediates. The activation energy (Ea) for 5–80% conversions was 213 kJ mol−1, and the pre-exponential factor (log A) was 24.34. Fast pyrolysis tests in a wire mesh reactor were conducted (300–650 °C). The formation of the liquid intermediate was visualized with a fast speed camera (250 Hz), showing the existence of three well defined steps: formation of lignin liquid intermediates, foaming and liquid intermediate swelling, and evaporation and droplet shrinking. GC/MS and UV-Fluorescence of the mesh reactor condensate revealed lignin oligomer formation but no mono-phenols were seen. An increase in pyrolytic lignin yield was observed as temperature increased. The molar mass determined by ESI-MS was not affected by pyrolysis temperature. SEM of the char showed a smooth surface with holes, evidence of a liquid intermediate with foaming; bursting from these foams could be responsible for the removal of lignin oligomers. Py-GC/MS studies showed the highest yield of guaiacol compounds at 450–550 °C.

AB - The formation of liquid intermediates and the distribution of products were studied under slow and fast pyrolysis conditions. Results indicate that monomers are formed from lignin oligomeric products during secondary reactions, rather than directly from the native lignin. Lignin from Douglas-fir (Pseudotsuga menziesii) wood was extracted using the milled wood enzyme lignin isolation method. Slow pyrolysis using a microscope with hot-stage captured the liquid formation (>150 °C), shrinking, swelling (foaming), and evaporation behavior of lignin intermediates. The activation energy (Ea) for 5–80% conversions was 213 kJ mol−1, and the pre-exponential factor (log A) was 24.34. Fast pyrolysis tests in a wire mesh reactor were conducted (300–650 °C). The formation of the liquid intermediate was visualized with a fast speed camera (250 Hz), showing the existence of three well defined steps: formation of lignin liquid intermediates, foaming and liquid intermediate swelling, and evaporation and droplet shrinking. GC/MS and UV-Fluorescence of the mesh reactor condensate revealed lignin oligomer formation but no mono-phenols were seen. An increase in pyrolytic lignin yield was observed as temperature increased. The molar mass determined by ESI-MS was not affected by pyrolysis temperature. SEM of the char showed a smooth surface with holes, evidence of a liquid intermediate with foaming; bursting from these foams could be responsible for the removal of lignin oligomers. Py-GC/MS studies showed the highest yield of guaiacol compounds at 450–550 °C.

KW - IR-96746

KW - METIS-311172

U2 - 10.1016/j.biombioe.2014.03.064

DO - 10.1016/j.biombioe.2014.03.064

M3 - Article

VL - 66

SP - 398

EP - 409

JO - Biomass & bioenergy

JF - Biomass & bioenergy

SN - 0961-9534

ER -