Thermal Decomposition Kinetics of Woods with an Emphasis on Torrefaction

The pyrolysis kinetics of Norwegian spruce and birch wood was studied to obtain information on the kinetics of torrefaction. Thermogravimetry (TGA) was employed with nine different heating programs, including linear, stepwise, modulated and constant reaction rate (CRR) experiments. The 18 experiments on the 2 feedstocks were evaluated simultaneously via the method of least-squares. Part of the kinetic parameters could be assumed common for both woods without a considerable worsening of the fit quality. This process results in better defined parameters and emphasizes the similarities between the woods. Three pseudo-components were assumed. Two of them were described by distributed activation energy models (DAEMs), while the decomposition of the cellulose pseudo-component was described by a self-accelerating kinetics. In another approach, the three pseudo-components were described by n-order reactions. Both approaches resulted in nearly the same fit quality, but the physical meaning of the model, based on three n-order reactions, was found to be problematic. The reliability of the models was tested by checking how well the experiments with higher heating rates can be described by the kinetic parameters obtained from the evaluation of a narrower subset of 10 experiments with slower heating. A table of data was calculated that may provide guidance about the extent of devolatilization at various temperature residence time values during wood torrefaction

Inputs of solid-state NMR to evaluate and compare thermal reactivity of pine and beech woods under torrefaction conditions and modified atmosphere

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NMR analysis of the transformation of wood constituents by torrefaction

International audienceThe injection of biomass in a pressurised entrained flow reactor is challenging. Biomass preparation by torrefaction before gasification could be a suitable option to improve it. Transformation of the material induced by this treatment lead to interesting features: increased brittleness, improved fluidisation properties of the powder, hydrophobicity, higher energy content. The major biomass constituents, cellulose, hemicelluloses and lignin are variously affected by torrefaction, depending on their respective reactivity. The objective of this work is to investigate the transformation of the biomass constitutive polymers induced by this thermal treatment. For that purpose, both solid-state NMR and EPR investigations have been performed on wood samples (beech) torrefied at different temperatures ranging from 200 °C to 300 °C. The results of these investigations have been compared with data obtained on untreated wood. These characterizations have brought to light different transformations of the polymers: de-acetylation of hemicelluloses, demethoxylation of lignin, changes in the cellulose structure. Furthermore, the temperature at which depolymerisation of the different components begins to occur has been identified

Pyrolysis of thick biomass particles: experimental and kinetic modeling

The aim of this work is to analyze some new experimental data of pyrolysis of thick woody biomass particles with the help of a general and comprehensive mathematical model. This multiphase and multiscale problem involves strong interactions between chemical kinetics, both in the solid and in the gas phase, and heat/mass transfer phenomena. Detailed experimental measurements have been obtained in an original lab scale reactor. This setup is designed to measure the products yielded along the pyrolysis of a single biomass (beech) particle as well as the temperature profiles into the sample. Experiments are carried out with pyrolysis temperatures ranging between 723 K and 1073 K. Lower-temperature pyrolysis data for poplar from a second reactor are also presented. These results constitute a very useful data set to tune and validate a predictive multistep kinetic model of biomass pyrolysis (Ranzi et al. 2008) and to analyse and discuss the relative effect of different phenomena. The thermal behavior of the pyrolysis process is particularly highlighted

Pelleting torrefied biomass at pilot-scale – Quality and implications for co-firing

The co-firing of solid biofuels in coal plants is an attractive and fast-track means of cutting emissions but its potential is linked to biomass densification. For torrefied materials this topic is under-represented in literature. This pilot-scale (121–203 kg h−1) pelleting study generated detailed knowledge on the densification of torrefied biomass compared to untreated biomass. Four feedstock with high supply availability (beech, poplar, wheat straw and corn cob) were studied in their untreated and torrefied forms. Systematic methods were used to produce 180 batches of 8 mm dia. pellets using press channel length (PCL) and moisture content (MC) ranges of 30–60 mm and 7.3–16.6% (wet basis) respectively. Analysis showed that moderate degrees of torrefaction (250–280 °C, 20–75 min) strongly affected pelleting behaviour. The highest quality black pellets had a mechanical durability and bulk density range of 87.5–98.7% and 662–697 kg m−3 respectively. Pelleting energy using torrefied feedstock varied from −15 to +53 kWh t−1 from untreated with increases in production fines. Optimal pelleting MC and PCL were reduced significantly for torrefied feedstock and pellet quality was characterised by a decrease in mechanical durability and an increase in bulk density. Energy densities of 11.9–13.2 GJ m−3 (as received) were obtained

Na+ and HTO diffusion in compacted bentonite: Effect of surface chemistry and related texture

International audienceIn underground repository concepts for radioactive waste, bentonite is studied as a reference swelling material to be used as an engineered barrier. Under the changing geochemical conditions prevailing within the barrier (saturation with the fluid coming from the host formation, diffusion of various chemical plumes caused by the degradation of some constituents of the barrier-system, etc.), the surface chemistry of the clay particles could evolve. This work aims to characterize the effects of these changes on (i) the microstructure of compacted bentonite samples and (ii) the diffusion properties of HTO and Na in these samples. For this purpose, bentonite sets were equilibrated with different solutions: NaCl, CaCl2, CsCl solutions as well as an artificial clayey porewater solution. The microstructure of the different samples was characterized by HRTEM and XRD, in a water saturated state. In parallel, effective diffusion coefficients of both HTO and 22Na were measured for the different samples. The density of the bentonite in the diffusion tests and in the HRTEM observations was set at 1.6 Mg m−3. From the microstructural observations and the results of diffusion tests, it is deduced that one key parameter is the occurrence of a gel phase in the material, which is found to depend strongly on the bentonite set: the gel phase dominates in Na-bentonite, while it is lacking in Cs-bentonite. The HTO diffusion coefficients are found to be lower in the samples with high gel phase content. Sodium diffusion does not follow the same trend: when compared with HTO, Na diffuses faster when the gel phase content is high. The latter result could indicate that the “accelerated diffusion mechanism” of cations, already mentioned in the literature, is enhanced in clayey materials that contain a gel phase