Subcritical water reactions of a hardwood derived organosolv lignin with nitrogen, hydrogen, carbon monoxide, and carbon dioxide gases

Meredith A. Hill Bembenic, Caroline E. Burgess Clifford

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Subcritical H 2O at 365 °C is considered for lignin conversion, because H 2O exhibits unusual properties at higher temperatures (i.e., decreased ion product and static dielectric constant), such that there is a high solubility for organic compounds. This high solubility for organic compounds is expected to apply to lignin for its conversion into high value transportation fuels, which may prove the effectiveness of integrated biorefineries. Experiments were conducted with hardwood derived Organosolv lignin, subcritical H 2O (defined here as H 2O at 365 °C and autogenous pressure), and various industrial gases (N 2, H 2, CO, and CO 2 at a cold pressure of 500 psi) for 30 min to determine both lignins potential to generate value-added products (e.g., monomer compounds and methanol) without the need for a catalyst and the roles (if any) of the H 2O and the gases in the reactions. The behavior of H 2O at temperature (365 °C) and pressure within this research is expected to be similar to the behavior of supercritical H 2O (374 °C and 3205 psi), without the need to maintain supercritical conditions. Different characterization techniques were used for the products collected including primarily gas chromatography with flame ionization detection and thermal conductivity detection (GC/FID-TCD) of the evolved gases, GC/MS analysis of the organic liquids, solid phase microextraction analysis of the recovered H 2O, and solid state 13C NMR analysis of the solid residues. The reactor pressure at temperature was shown to influence the outcome of products, and the highest conversions (≈54-62%) were obtained when adding gas. The collected solids from the N 2, H 2, and CO reactions appeared to be the most reacted (i.e., the most changed from the unreacted lignin) according to solid state 13C NMR analysis, and the widest variety of products (methoxy-substituted phenolic compounds) were also obtained when using CO, according to GC/MS analysis.

Original languageEnglish (US)
Pages (from-to)4540-4549
Number of pages10
JournalEnergy and Fuels
Volume26
Issue number7
DOIs
StatePublished - Jul 19 2012

Fingerprint

Lignin
Hardwoods
Carbon Monoxide
Carbon Dioxide
Carbon monoxide
Hydrogen
Carbon dioxide
Nitrogen
Gases
Water
Organic compounds
Solubility
Nuclear magnetic resonance
Gas chromatography
Temperature
Ionization
Methanol
Thermal conductivity
Permittivity
Monomers

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)
  • Fuel Technology
  • Energy Engineering and Power Technology

Cite this

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title = "Subcritical water reactions of a hardwood derived organosolv lignin with nitrogen, hydrogen, carbon monoxide, and carbon dioxide gases",
abstract = "Subcritical H 2O at 365 °C is considered for lignin conversion, because H 2O exhibits unusual properties at higher temperatures (i.e., decreased ion product and static dielectric constant), such that there is a high solubility for organic compounds. This high solubility for organic compounds is expected to apply to lignin for its conversion into high value transportation fuels, which may prove the effectiveness of integrated biorefineries. Experiments were conducted with hardwood derived Organosolv lignin, subcritical H 2O (defined here as H 2O at 365 °C and autogenous pressure), and various industrial gases (N 2, H 2, CO, and CO 2 at a cold pressure of 500 psi) for 30 min to determine both lignins potential to generate value-added products (e.g., monomer compounds and methanol) without the need for a catalyst and the roles (if any) of the H 2O and the gases in the reactions. The behavior of H 2O at temperature (365 °C) and pressure within this research is expected to be similar to the behavior of supercritical H 2O (374 °C and 3205 psi), without the need to maintain supercritical conditions. Different characterization techniques were used for the products collected including primarily gas chromatography with flame ionization detection and thermal conductivity detection (GC/FID-TCD) of the evolved gases, GC/MS analysis of the organic liquids, solid phase microextraction analysis of the recovered H 2O, and solid state 13C NMR analysis of the solid residues. The reactor pressure at temperature was shown to influence the outcome of products, and the highest conversions (≈54-62{\%}) were obtained when adding gas. The collected solids from the N 2, H 2, and CO reactions appeared to be the most reacted (i.e., the most changed from the unreacted lignin) according to solid state 13C NMR analysis, and the widest variety of products (methoxy-substituted phenolic compounds) were also obtained when using CO, according to GC/MS analysis.",
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Subcritical water reactions of a hardwood derived organosolv lignin with nitrogen, hydrogen, carbon monoxide, and carbon dioxide gases. / Hill Bembenic, Meredith A.; Burgess Clifford, Caroline E.

In: Energy and Fuels, Vol. 26, No. 7, 19.07.2012, p. 4540-4549.

Research output: Contribution to journalArticle

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