Thermochemical characterisation of straws and high yielding perennial grasses

The research is concerned with thermochemical characterisation of straws and high yielding perennial grasses. Crops selected for this study include wheat straw (Triticum aestivum), rape straw (Brassica napus), reed canary grass (Phalaris arundinacea) and switch grass (Panicum virgatum). Thermogravimetric analysis (TGA) was used to examine the distribution of char and volatiles during pyrolysis up to 900 °C. Utilising multi-heating rate thermogravimetric data, the Friedman iso-conversional kinetic method was used to determine pyrolysis kinetic parameters. Light and medium volatile decomposition products were investigated using pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS) up to 520 °C. The 22 highest yielding identifiable cellulose, hemicellulose and lignin biomass markers were semi-quantified taking into consideration peak areas from GC chromatograms. Notable differences can be seen in butanedioic acid, dimethyl ester (hemicelluloses decomposition products), 2-methoxy-4-vinylphenol (lignin marker) and levoglucosan (intermediate pyrolytic decomposition product of cellulose) content when comparing perennial grasses with straw. From results presented in this study, perennial grasses such as switch grass, have the most attractive properties for fast pyrolysis processing. This is because of the observed high volatile yield content of 82.23%, heating value of 19.64 MJ/kg and the relatively low inorganic content.

Quantification of hydroxycinnamic acids and lignin in perennial forage and energy grasses by Fourier-transform infrared spectroscopy and partial least squares regression

Levels of lignin and hydroxycinnamic acid wall components in three genera of forage grasses (Lolium,Festuca and Dactylis) have been accurately predicted by Fourier-transform infrared spectroscopy using partial least squares models correlated to analytical measurements. Different models were derived that predicted the concentrations of acid detergent lignin, total hydroxycinnamic acids, total ferulate monomers plus dimers, p-coumarate and ferulate dimers in independent spectral test data from methanol extracted samples of perennial forage grass with accuracies of 92.8%, 86.5%, 86.1%, 59.7% and 84.7% respectively, and analysis of model projection scores showed that the models relied generally on spectral features that are known absorptions of these compounds. Acid detergent lignin was predicted in samples of two species of energy grass, (Phalaris arundinacea and Pancium virgatum) with an accuracy of 84.5%.

Nitrogen cycle of effluent-irrigated energy crop plantations:from wastewater treatment to thermo-chemical conversion processes

This paper reviews nitrogen (N) cycle of effluent-irrigated energy crop plantations, starting from wastewater treatment to thermo-chemical conversion processes. In wastewater, N compounds contribute to eutrophication and toxicity in water cycle. Removal of N via vegetative filters and specifically in short-rotation energy plantations, is a relatively new approach to managing nitrogenous effluents. Though combustion of energy crops is in principle carbon neutral, in practice, N content may contribute to NOx emissions with significant global warming potential. Intermediate pyrolysis produces advanced fuels while reducing such emissions. By operating at intermediate temperature (500°C), it retains most N in char as pyrrolic-N, pyridinic-N, quaternary-N and amines. In addition, biochar provides long-term sequestration of carbon in soils.

Prediction of Klason lignin and lignin thermal degradation products by Py-GC/MS in a collection of Lolium and Festuca grasses

A rapid method for the analysis of biomass feedstocks was established to identify the quality of the pyrolysis products likely to impact on bio-oil production. A total of 15 Lolium and Festuca grasses known to exhibit a range of Klason lignin contents were analysed by pyroprobe-GC/MS (Py-GC/MS) to determine the composition of the thermal degradation products of lignin. The identification of key marker compounds which are the derivatives of the three major lignin subunits (G, H, and S) allowed pyroprobe-GC/MS to be statistically correlated to the Klason lignin content of the biomass using the partial least-square method to produce a calibration model. Data from this multivariate modelling procedure was then applied to identify likely "key marker" ions representative of the lignin subunits from the mass spectral data. The combined total abundance of the identified key markers for the lignin subunits exhibited a linear relationship with the Klason lignin content. In addition the effect of alkali metal concentration on optimum pyrolysis characteristics was also examined. Washing of the grass samples removed approximately 70% of the metals and changed the characteristics of the thermal degradation process and products. Overall the data indicate that both the organic and inorganic specification of the biofuel impacts on the pyrolysis process and that pyroprobe-GC/MS is a suitable analytical technique to asses lignin composition. © 2007 Elsevier B.V. All rights reserved.