In kraft pulp mills, black liquor is concentrated and burned in recovery boilers to produce steam and power and to recover pulping chemicals. Black liquor contains a large amount of alkali compounds, which form ash with low melting temperatures upon combustion. This causes many problems in recovery boiler operation, including fouling of the heat transfer surfaces, plugging of the flue gas passages, reduction of the heat transfer rate, and corrosion of the superheater tubes. This paper presents a model for simulating fine fume particles formed as a result of condensation of alkali compound vapors in the recovery boiler. The modeling method combines CFD modeling, equilibrium chemistry, and fine particle dynamics in a way that enables simulation of a full scale three-dimensional boiler environment. The model has been partially validated with measurements performed in an operating recovery boiler. The modeling results, particularly for the fume particle composition, agree well with the actual measurements. (C) 2014 Elsevier Ltd. All rights reserved.