Lignin depolymerisation in supercritical carbon dioxide/acetone/water fluid for the production of aromatic chemicals.

Valorisation of lignin plays a key role in further development of lignocellulosic biorefinery processes the production of biofuels and bio-based materials. In the present study, organosolv hardwood and wheat straw lignins were converted in a supercritical fluid consisting of carbon dioxide/acetone/water (300-370°C, 100bar) to a phenolic oil consisting of oligomeric fragments and monomeric aromatic compounds with a total yield of 10-12% based on lignin. These yields are similar to the state-of-the-art technologies such as base-catalysed thermal processes applied for lignin depolymerisation. Addition of formic acid increases the yield of monomeric aromatic species by stabilizing aromatic radicals. Supercritical depolymerisation of wheat straw and hardwood lignin yielded monomeric compounds in different compositions with a maximum yield of 2.0% for syringic acid and 3.6% for syringol, respectively. The results of the present study showed that under the applied conditions competition occurred between lignin depolymerisation and recondensation of fragments.

[1]  Paul C. Struik,et al.  Securing renewable resource supplies for changing market demands in a bio-based economy , 2005 .

[2]  Phillip E. Savage,et al.  Decomposition of Formic Acid under Hydrothermal Conditions , 1998 .

[3]  Mathieu F. Bilodeau,et al.  Depolymerization of steam-treated lignin for the production of green chemicals. , 2011, Bioresource technology.

[4]  Seiichi Takami,et al.  Disassembly of lignin and chemical recovery—rapid depolymerization of lignin without char formation in water–phenol mixtures , 2004 .

[5]  D. Stewart Lignin as a base material for materials applications: Chemistry, application and economics , 2008 .

[6]  Xi-qi Feng,et al.  Characteristics of the optical absorption edge and defect structures of La3+-doped PbWO4 crystals , 2004 .

[7]  Charlotte K. Williams,et al.  The Path Forward for Biofuels and Biomaterials , 2006, Science.

[8]  M. Umetsu,et al.  Efficient conversion of lignin into single chemical species by solvothermal reaction in water–p-cresol solvent , 2004 .

[9]  B. Weckhuysen,et al.  The catalytic valorization of lignin for the production of renewable chemicals. , 2010, Chemical reviews.

[10]  James E. Miller,et al.  Batch microreactor studies of lignin and lignin model compound depolymerization by bases in alcohol solvents , 1999 .

[11]  C. Xu,et al.  Hydrolytic degradation of alkaline lignin in hot-compressed water and ethanol. , 2010, Bioresource technology.

[12]  T. Barth,et al.  Phenols from Lignin , 2008 .

[13]  J. Sanders,et al.  Fractionation, analysis, and PCA modeling of properties of four technical lignins for prediction of their application potential in binders , 2010 .

[14]  T. Barth,et al.  Optimizing solvolysis conditions for integrated depolymerisation and hydrodeoxygenation of lignin to produce liquid biofuel. , 2009 .

[15]  Ayhan Demirbas,et al.  Yields of oil products from thermochemical biomass conversion processes , 1998 .

[16]  Ronald W. Thring,et al.  The production of gasoline range hydrocarbons from Alcell® lignin using HZSM-5 catalyst , 2000 .

[17]  Fu-Shen Zhang,et al.  Effects of various solvents on the liquefaction of biomass to produce fuels and chemical feedstocks , 2008 .

[18]  C. Roy,et al.  Production of monomeric phenols by thermochemical conversion of biomass: a review. , 2001, Bioresource technology.

[19]  Chang-Soo Kim,et al.  Lignin Depolymerization and Conversion: A Review of Thermochemical Methods , 2011 .

[20]  S. Oh,et al.  Kinetics of the degradation of polystyrene in supercritical acetone , 2007 .

[21]  Johan P.M. Sanders,et al.  Bulk chemicals from biomass , 2008 .

[22]  Ioannis V. Skiadas,et al.  Toward a common classification approach for biorefinery systems , 2009 .

[23]  A. Contin,et al.  Complementare/Lezione 2/Top Value-Added Chemicals from Biomass, Volume II: Results of Screening for Potential, Candidates from Biorefinery Lignin, PNNL-16983 (2007) , 2012 .

[24]  S. Saka,et al.  Reaction behavior of lignin in supercritical methanol as studied with lignin model compounds , 2003, Journal of Wood Science.