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Quick and reliable inorganic elemental chemical analysis of biomass (incl. solid biofuels) is of importance in the increasing utilization and trade of biomass. In particular, it is important for the exploitation of contaminated / dirty biomass / biomass waste, and potentially also as a tool in ascertaining the type/origin of biomass. X-ray fluorescence (XRF) spectrometry performed directly on the raw biomass with limited prior sample preparation is an attractive method for performing such inorganic elemental analysis. In the present study we therefore carefully investigate the performance of a commercial multi-element standardless XRF method by analyzing 5 common biomass types (switchgrass, corn stover, eucalyptus, beech, and pine wood). Sample preparation involves milling the raw biomass using cutter and rotor mills (avoiding ball-milling) and cold-pressing the powdered samples into pellets using binder (vax).XRF users often rely on this type of commercial pre-calibrated or 'standardless' methods delivered with their XRF spectrometer. However, these methods are often sold without any guarantee on performance. We recently demonstrated the quite good performance of a typical commercial pre-calibrated / standardless method when analyzing biomass in the ideal form of certified reference material. In the present article, we report now on analysis of common raw biomass using the same method purchased with a 4 kW wavelength dispersive (WD) XRF spectrometer. The accuracy (trueness and precision) is determined by comparing the XRF data with the elemental composition obtained by standard elemental analysis (ICP-OES and ionchromatography). The certified elements consistently detected by the XRF are: Na, Mg, Al, Si, P, S, Cl, K, Ca, Mn, Fe, Co, Ni, Cu, Zn, Sr, Mo. For elements above 25 ppm, the XRF data show a relative systematic error (bias, trueness) typically better than ±15% independent of the concentration. The elements present with > 1000 ppm (Mg, Si, Cl, K, Ca) consistently show a positive bias of 3 -18% relative. The relative precision (measured as the relative standard error) is better than ±5% (typically ±1%) for concentrations > 25 ppm (obtained with 10 -30 measurements). Quantifying elements below 25 ppm (Co, Ni, Cu, Zn, Sr, Mo) is possible in some cases, but it requires a more detailed study for each specific element. E.g. Cu can be determined down to a few ppm with an appropriate correction for the method bias. Occasionally, larger relative biases of up to 45% to 90% can occur for certain elements (Cl, Si) in certain samples, so care should be taken to carefully test the applied method for the particular samples and elements of interest. Quantification of silicon (Si) by XRF works well for concentrations > 100 ppm. The XRF method can further be used to estimate the ash yield from biomass combustion with a relative bias better than ±10%.It is shown that the errors on the elemental composition are dominated by systematic errors (biases) and therefore measuring the two sides of a single pellet combined with corre...

The effects of mineral-acid doping on the long-term reactivity of limestone-based sorbents for CO2 capture was investigated in this work. Havelock (Canada), Longcliffe (U.K.), and Purbeck (U.K.) limestones were doped with a range of mineral acids (HCl, HBr, HI, and HNO3), and the effects of concentration were also studied. Doped samples were subjected to repeated cycles of carbonation and calcination in a fluidized-bed reactor. The experimental results showed that HBr and HCl as dopants with a 0.167 mol % doping concentration significantly improved the long-term reactivity of Havelock and Longcliffe limestones (doping with HI marginally improved the reactivity); however, doping Havelock limestone with a similar concentration of HNO3 reduced its CO2 uptake. Purbeck limestone was not significantly improved in reactivity by any dopant. Gas adsorption analyses showed that sorbents have a very small surface area: less than 4 m2/g. The pore size distribution appears to change significantly upon doping for those sorbents that are improved by doping, and it is likely that optimizing the pore size distribution upon cycling is one reason for the enhanced reactivity observed. The pore-size distributions of the initially calcined limestones and the changes thereof with cycling and doping explain the differences in the behaviors of the limestones.

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RESUMO-This work aimed at comparing the gasification potential of rice husk samples from Brazil (CAZ1) and Thailand (CAZ2). The pyrolysis step was performed in two pyrolysis reactors under different conditions. The product yields were determined and related to the pyrolysis conditions applied. The biomass and rice husk chars were characterized and overall char combustion and gasification reactivities were measured by thermogravimetry in synthetic air and in CO2, respectively. The differences in samples properties play important roles in the thermochemical conversion steps. These differences may reflect local variations of the agricultural growing conditions, as noticed between the two rice husk samples studied, being the Thai rice husk char more reactive than the Brazilian one both in air and CO2 gasification.