Due to the urgent needs to reduce anthropogenic carbon dioxide emissions there is an increasing interest in the use of alternative fuels. For this reason, there is a need for new knowledge on how to design and adapt existing heat and power plants to biogenic and waste-derived fuels. This work relates to co-firing of biomass and coal and the sulfation of alkali chlorides in coal-fired flames doped with chemical additives. We aim to examine the global time scales of alkali sulfation and chlorination based on combustion experiments that were conducted in a 30-kW coal flame. Temperature, gas and particle composition measurements were conducted. Both experiments and modelling support that the apparent alkali sulfation kinetics are fast in a coal-fired flame and that it is dominated entirely by the presence of SO2. The availability of oxygen and carbon monoxide, or hydrocarbons, is also critical to sustain the sulfation reaction cycle; low concentrations are sufficient. For industrial boilers this implies that sulfur addition, in combination with reburning, should constitute an efficient strategy to mitigate alkali-chlorination and the related high temperature corrosion.