The effect of lignin and inorganic species in biomass on pyrolysis oil yields, quality and stability

This paper investigates four reference fuels and three low lignin Lolium Festuca grasses which were subjected to pyrolysis to produce pyrolysis oils. The oils were analysed to determine their quality and stability, enabling the identification of feedstock traits which affect oil stability. Two washed feedstocks were also subjected to pyrolysis to investigate whether washing can enhance pyrolysis oil quality. It was found that the mineral matter had the dominate effect on pyrolysis in compared to lignin content, in terms of pyrolysis yields for organics, char and gases. However the higher molecular weight compounds present in the pyrolysis oil are due to the lignin derived compounds as determined by results of GPC and liquid-GC/MS. The light organic fraction also increased in yield, but reduced in water content as metals increased at the expense of the lignin content. It was found that the fresh oil and aged oil had different compound intensities/concentrations, which is due to a large number of reactions occurring when the oil is aged day by day. These findings agree with previous reports which suggest that a large amount of re-polymerisation occurs as levoglucosan yields increase during the aging progress, while hydroxyacetaldehyde decrease. In summary the paper reports a window for producing a more stable pyrolysis oil by the use of energy crops, and also show that washing of biomass can improve oil quality and stability for high ash feedstocks, but less so for the energy crops.

[1]  A. Bridgwater,et al.  Fast pyrolysis processes for biomass , 2000 .

[2]  Anja Oasmaa,et al.  Characterization of biomass-based flash pyrolysis oils , 1998 .

[3]  A. Bridgwater,et al.  An overview of fast pyrolysis of biomass , 1999 .

[4]  D. Meier,et al.  Discrimination of genetically modified poplar clones by analytical pyrolysis–gas chromatography and principal component analysis , 2005 .

[5]  Anthony V. Bridgwater,et al.  Principles and practice of biomass fast pyrolysis processes for liquids , 1999 .

[6]  G. Fang,et al.  A study of polycyclic aromatic hydrocarbons concentrations and source identifications by methods of diagnostic ratio and principal component analysis at Taichung chemical Harbor near Taiwan Strait. , 2006, Chemosphere.

[7]  Anthony V. Bridgwater,et al.  Fast pyrolysis of biomass : a handbook , 1999 .

[8]  P. James McLellan,et al.  A functional-PCA approach for analyzing and reducing complex chemical mechanisms , 2006, Comput. Chem. Eng..

[9]  Ablative pyrolysis of biomass , 1994 .

[10]  Dietrich Meier,et al.  Characterization of the water-insoluble fraction from pyrolysis oil (pyrolytic lignin). Part I. PY–GC/MS, FTIR, and functional groups , 2001 .

[11]  M. Statheropoulos,et al.  PCA-ContVarDia : an improvement of the PCA-VarDia technique for curve resolution in GC-MS and TG-MS analysis , 2001 .

[12]  Iain S. Donnison,et al.  Prediction of Klason lignin and lignin thermal degradation products by Py-GC/MS in a collection of Lolium and Festuca grasses , 2007 .

[13]  Thomas A. Milne,et al.  Molecular characterization of the pyrolysis of biomass , 1987 .

[14]  Iain S. Donnison,et al.  The effect of alkali metals on combustion and pyrolysis of Lolium and Festuca grasses, switchgrass and willow , 2007 .

[15]  E. Jakab,et al.  Thermal decomposition of mixtures of vinyl polymers and lignocellulosic materials , 2001 .

[16]  Thomas A. Milne,et al.  Molecular characterization of the pyrolysis of biomass. 2. Applications , 1987 .

[17]  R. Hague The pre-treatment and pyrolysis of biomass for the production of liquids for fuels and speciality chemicals , 1998 .

[18]  Dietrich Meier,et al.  Norms and standards for fast pyrolysis liquids: 1. Round robin test , 2005 .

[19]  Andrew B. Ross,et al.  Potassium catalysis in the pyrolysis behaviour of short rotation willow coppice , 2007 .

[20]  K. Khilar,et al.  Influence of mineral matter on biomass pyrolysis characteristics , 1995 .

[21]  F. Berruti,et al.  A KINETIC MODEL FOR THE PRODUCTION OF LIQUIDS FROM THE FLASH PYROLYSIS OF BIOMASS , 1988 .

[22]  D. Meier,et al.  Characterization of Residual Lignins from Chemical Pulps of Spruce (Picea abies L.) and Beech (Fagus sylvatica L.) by Analytical Pyrolysis–Gas Chromatography/Mass Spectrometry , 2001 .

[23]  A. Oasmaa,et al.  Fast Pyrolysis of Forestry Residue. 3. Storage Stability of Liquid Fuel , 2003 .

[24]  M. Antal Effects of reactor severity on the gas-phase pyrolysis of cellulose- and kraft lignin-derived volatile matter , 1983 .

[25]  M. Antal,et al.  A Review of the Vapor Phase Pyrolysis of Biomass Derived Volatile Matter , 1985 .

[26]  Anthony V. Bridgwater,et al.  Renewable fuels and chemicals by thermal processing of biomass , 2003 .

[27]  Fred Shafizadeh,et al.  A kinetic model for pyrolysis of cellulose. , 1979 .

[28]  A. Bridgwater,et al.  Overview of Applications of Biomass Fast Pyrolysis Oil , 2004 .

[29]  J. P. Diebold,et al.  A review of the chemical and physical mechanisms of the storage stability of fast pyrolysis bio-oils , 1999 .