The formation of CH3Cl and the transformation of chlorine and potassium during pyrolysis of biomass were investigated. Model biomass compounds (cellulose, xylan, lignin and pectin) and pine wood doped with KCl were pyrolysed in a TGA at different heating rates (10-1000 degrees C/ min), temperatures (300-850 degrees C), and KCl contents (0-5 wt%). The volatiles were collected and analyzed for CH3Cl concentration by GC-MS. The solid residue was analyzed by ICP-OES for the contents of total and water soluble K and Cl. Considerable amounts of CH3Cl, corresponding to 20-50% of the fuel chlorine, were formed in pyrolysis of KCl doped pine wood, lignin and pectin samples, suggesting a methylation ability of these biomass on KCl by their methoxyl groups. Lignin and pine wood could supply methoxyl groups for reaction with as much as about 2% KCl doping, and pectin had an even greater capacity. Organic K was found in the solid residue of all samples, further supporting the occurrence of reactions between KCl and the organic matrix in biomass. With a holding temperature of 500 degrees C, an increase of heating rate from 10 degrees C/min to 500 degrees C/min significantly reduced the yield of CH3Cl from KCl doped wood/lignin/pectin, while no further reduction effect was observed at 1000 degrees C/min. For a heating rate of 500 degrees C/min, an increase of holding temperature from 300 degrees C to 850 degrees C caused a decreased yield of CH3Cl. (C) 2017 Elsevier Ltd. All rights reserved.