The release of chlorine (Cl) and sulfur (S) during biomass torrefaction and pyrolysis has been investigated via experiments in two laboratory-scale reactors: a rotating reactor and a fixed bed reactor. Six biomasses with different chemical compositions covering a wide range of ash content and ash-forming elements were torrefied/pyrolyzed in the temperature range of 150−500 °C. The relative release of chlorine and sulfur was calculated based on mass balance and analysis of the biomass before and after torrefaction. In selected cases, measurement of methyl chloride (CH 3 Cl) in the gas from straw torrefaction has furthermore been conducted. The release of chlorine from straw was first observed at 250 °C and peaked with about 60−70% at 350 °C. Analysis of the released gas showed that most of the chlorine was released as methyl chloride. Increasing the straw content in the reactor resulted in a lower fractional release of Cl, probably due to more reactive sites in contact with gas phase Cl species leading to secondary binding of Cl to the solid product. Almost complete release of chlorine was observed for woody biomass at 350 °C. This result is in agreement with previous studies reporting that biomasses with a lower chlorine content release a higher fraction of chlorine during the pyrolysis process. A significant sulfur release (about 60%) was observed from the six biomasses investigated at 350 °C. The initial sulfur content in the biomass did not influence the fraction of sulfur release during torrefaction.
Different biomass types may differ with respect to torrefaction characteristics, and an improved understanding and ability to predict the torrefaction performance is, therefore, desired. In this study, the influence of the chemical properties (lignocellulose composition and alkali content) on the torrefaction behavior with respect to mass loss and grindability is investigated by simultaneous thermal analysis (STA) and by using a combined torrefaction and grinding reactor. The torrefaction behavior of six raw biomass samples and selected pretreated samples (washed and impregnated with KCl and K2CO3) has been studied. The investigated biomasses have reasonably similar carbohydrate compositions (hemicelluloses 18–25 wt % db; cellulose 38–48 wt % db; lignin 17–29 wt % db) with the exception of spruce bark, which is lower in hemicellulose content (12.9 wt % db) and cellulose content (24 wt % db), and higher in lignin content (36.8 wt % db). An increasing biomass potassium (K) content decreases the temperature of maximal conversion for both raw and alkali-impregnated biomass samples, thus decreasing the solid product yield at 270 and 300 °C. This was especially pronounced when the biomass potassium content increased from 0 to 0.2 wt %. However, the higher lignin content in bark causes a higher solid yield than what would be expected from the alkali content, illustrating that both potassium content and lignocellulose composition affect the solid yield obtained by torrefaction. The grindability of the torrefied products was evaluated by determining the d50 value of the particle size distribution of the biomass before and after torrefaction in the combined torrefaction and mill reactor. A significant decrease in d50 value was observed when the alkali content increased from 0 to 0.2 wt % db, whereas no additional effect is seen for higher potassium contents.
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