Catalytic upgrading of lignocellulosic biomass pyrolysis vapours: Effect of hydrothermal pre-treatment of biomass

S. Stephanidis, C. Nitsos, K. Kalogiannis, E. F. Iliopoulou, A. A. Lappas, K. S. Triantafyllidis*

*Corresponding author for this work

Research output: Contribution to journalArticle

Abstract

The main objective of the present work was the study of the effect of hydrothermal pretreatment of lignocellulosic biomass (beech wood) on the product yields and bio-oil composition produced from biomass flash pyrolysis as well as from the catalytic upgrading of the biomass pyrolysis vapours. The hydrothermal pretreatment of lignocellulosic biomass was performed at a severity factor (Ro) of 3.55 leading to ∼35 wt.% loss of solids, mainly due to solubilization and removal of hemicellulose. The production of sugars (mainly levoglucosan) was significantly increased by the use of the hydrothermally pretreated biomass instead of the untreated biomass in the non-catalytic flash pyrolysis experiments. On the other hand, the concentration of carboxylic acids, ketones and phenols was decreased in the bio-oil derived from the pretreated biomass. The catalysts tested in the upgrading of the biomass pyrolysis vapours were the strongly acidic zeolites H-ZSM-5 and silicalite (with very low number of acid sites) and the mildly acidic mesoporous aluminosilicate Al-MCM-41. The effect of catalysts on product yields and composition of bio-oil in the upgrading of pyrolysis vapours, was similar for both the pretreated and untreated biomass. The use of zeolite H-ZSM-5 decreased the total liquid yield (bio-oil) via decreasing the organic phase of bio-oil and increasing its water content, accompanied by increase of gases and moderate formation of coke on the catalyst. The zeolite silicalite and the Al-MCM-41 induced similar effects with those of H-ZSM-5 but to a less extent, except of the significantly higher coke that was deposited on Al-MCM-41. With regard to the composition of the bio-oil, all the catalysts and mostly the strongly acidic H-ZSM-5 zeolite reduced the oxygen content of the organic fraction, mainly by decreasing the concentration of acids, ketones and phenols in the untreated biomass pyrolysis oil or the concentration of sugars in the pretreated biomass pyrolysis oil. Aromatics and polycyclic aromatic hydrocarbons (PAHs) were significantly increased by the use of all catalysts, for both types of biomass feed. A substantial increase in the concentration of phenols was observed in the upgraded bio-oil derived by the hydrothermally pretreated biomass, using the less acidic silicalite and Al-MCM-41 catalysts.

Original languageEnglish
Pages (from-to)37-45
Number of pages9
JournalCatalysis Today
Volume167
Issue number1
DOIs
Publication statusPublished - 10 Jun 2011

Fingerprint

Biomass
Pyrolysis
Vapors
Oils
Multicarrier modulation
Zeolites
Catalysts
Phenols
Ketones
Coke
Sugars
Chemical analysis
Acids
Aluminosilicates
Polycyclic Aromatic Hydrocarbons
Polycyclic aromatic hydrocarbons
Carboxylic Acids
Carboxylic acids
Water content
Wood

Keywords

  • Bio-oil
  • Biomass flash pyrolysis
  • Catalytic upgrading
  • De-oxygenation
  • Hydrothermal pretreatment of biomass
  • Levoglucosan
  • Lignocellulosic wood biomass
  • Mesoporous Al-MCM-41
  • Phenols
  • Zeolites H-ZSM-5/silicalite

Cite this

Stephanidis, S. ; Nitsos, C. ; Kalogiannis, K. ; Iliopoulou, E. F. ; Lappas, A. A. ; Triantafyllidis, K. S. / Catalytic upgrading of lignocellulosic biomass pyrolysis vapours : Effect of hydrothermal pre-treatment of biomass. In: Catalysis Today. 2011 ; Vol. 167, No. 1. pp. 37-45.
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Catalytic upgrading of lignocellulosic biomass pyrolysis vapours : Effect of hydrothermal pre-treatment of biomass. / Stephanidis, S.; Nitsos, C.; Kalogiannis, K.; Iliopoulou, E. F.; Lappas, A. A.; Triantafyllidis, K. S.

In: Catalysis Today, Vol. 167, No. 1, 10.06.2011, p. 37-45.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Catalytic upgrading of lignocellulosic biomass pyrolysis vapours

T2 - Effect of hydrothermal pre-treatment of biomass

AU - Stephanidis, S.

AU - Nitsos, C.

AU - Kalogiannis, K.

AU - Iliopoulou, E. F.

AU - Lappas, A. A.

AU - Triantafyllidis, K. S.

PY - 2011/6/10

Y1 - 2011/6/10

N2 - The main objective of the present work was the study of the effect of hydrothermal pretreatment of lignocellulosic biomass (beech wood) on the product yields and bio-oil composition produced from biomass flash pyrolysis as well as from the catalytic upgrading of the biomass pyrolysis vapours. The hydrothermal pretreatment of lignocellulosic biomass was performed at a severity factor (Ro) of 3.55 leading to ∼35 wt.% loss of solids, mainly due to solubilization and removal of hemicellulose. The production of sugars (mainly levoglucosan) was significantly increased by the use of the hydrothermally pretreated biomass instead of the untreated biomass in the non-catalytic flash pyrolysis experiments. On the other hand, the concentration of carboxylic acids, ketones and phenols was decreased in the bio-oil derived from the pretreated biomass. The catalysts tested in the upgrading of the biomass pyrolysis vapours were the strongly acidic zeolites H-ZSM-5 and silicalite (with very low number of acid sites) and the mildly acidic mesoporous aluminosilicate Al-MCM-41. The effect of catalysts on product yields and composition of bio-oil in the upgrading of pyrolysis vapours, was similar for both the pretreated and untreated biomass. The use of zeolite H-ZSM-5 decreased the total liquid yield (bio-oil) via decreasing the organic phase of bio-oil and increasing its water content, accompanied by increase of gases and moderate formation of coke on the catalyst. The zeolite silicalite and the Al-MCM-41 induced similar effects with those of H-ZSM-5 but to a less extent, except of the significantly higher coke that was deposited on Al-MCM-41. With regard to the composition of the bio-oil, all the catalysts and mostly the strongly acidic H-ZSM-5 zeolite reduced the oxygen content of the organic fraction, mainly by decreasing the concentration of acids, ketones and phenols in the untreated biomass pyrolysis oil or the concentration of sugars in the pretreated biomass pyrolysis oil. Aromatics and polycyclic aromatic hydrocarbons (PAHs) were significantly increased by the use of all catalysts, for both types of biomass feed. A substantial increase in the concentration of phenols was observed in the upgraded bio-oil derived by the hydrothermally pretreated biomass, using the less acidic silicalite and Al-MCM-41 catalysts.

AB - The main objective of the present work was the study of the effect of hydrothermal pretreatment of lignocellulosic biomass (beech wood) on the product yields and bio-oil composition produced from biomass flash pyrolysis as well as from the catalytic upgrading of the biomass pyrolysis vapours. The hydrothermal pretreatment of lignocellulosic biomass was performed at a severity factor (Ro) of 3.55 leading to ∼35 wt.% loss of solids, mainly due to solubilization and removal of hemicellulose. The production of sugars (mainly levoglucosan) was significantly increased by the use of the hydrothermally pretreated biomass instead of the untreated biomass in the non-catalytic flash pyrolysis experiments. On the other hand, the concentration of carboxylic acids, ketones and phenols was decreased in the bio-oil derived from the pretreated biomass. The catalysts tested in the upgrading of the biomass pyrolysis vapours were the strongly acidic zeolites H-ZSM-5 and silicalite (with very low number of acid sites) and the mildly acidic mesoporous aluminosilicate Al-MCM-41. The effect of catalysts on product yields and composition of bio-oil in the upgrading of pyrolysis vapours, was similar for both the pretreated and untreated biomass. The use of zeolite H-ZSM-5 decreased the total liquid yield (bio-oil) via decreasing the organic phase of bio-oil and increasing its water content, accompanied by increase of gases and moderate formation of coke on the catalyst. The zeolite silicalite and the Al-MCM-41 induced similar effects with those of H-ZSM-5 but to a less extent, except of the significantly higher coke that was deposited on Al-MCM-41. With regard to the composition of the bio-oil, all the catalysts and mostly the strongly acidic H-ZSM-5 zeolite reduced the oxygen content of the organic fraction, mainly by decreasing the concentration of acids, ketones and phenols in the untreated biomass pyrolysis oil or the concentration of sugars in the pretreated biomass pyrolysis oil. Aromatics and polycyclic aromatic hydrocarbons (PAHs) were significantly increased by the use of all catalysts, for both types of biomass feed. A substantial increase in the concentration of phenols was observed in the upgraded bio-oil derived by the hydrothermally pretreated biomass, using the less acidic silicalite and Al-MCM-41 catalysts.

KW - Bio-oil

KW - Biomass flash pyrolysis

KW - Catalytic upgrading

KW - De-oxygenation

KW - Hydrothermal pretreatment of biomass

KW - Levoglucosan

KW - Lignocellulosic wood biomass

KW - Mesoporous Al-MCM-41

KW - Phenols

KW - Zeolites H-ZSM-5/silicalite

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