Additonal authors: Viitala, H.. Book title: Proceedings of the 58th Conference of Metallurgists Hosting Copper 2019. Chapter: . Chapter title:
The formation of copper chlorides in flue dust or deposits in heat recovery boiler of copper smelters or waste-fired boilers may lead to formation of corrosive partially molten deposits on walls and heat exchangers of the boilers. These deposits can contain various other metals, such as alkalis, Fe, Zn, Pb together with oxides and sulfates. In the present study, a thermodynamic model for copper-containing binary and ternary metal chloride systems within multicomponent CuCl-CuCl2-FeCl2-FeCl3- PbCl2-ZnCl2 system has been assessed and optimized based on own experimental phase equilibrium data, as well as literature data. The thermodynamic properties of the liquid phase was modelled using the quasichemical quadruplet model and a thermodynamic database was optimized to predict all available experimental data within the experimental error limits. The thermodynamic database allows for more accurate predictions of potential corrosion-related issues in various heat recovery boilers and waste-fired boilers due to formation of copper chlorides.
INTRODUCTION
In the copper flash smelting, flue dust can cause severe problems in the gas train, used for separating dust from the SO2-rich off gas, by forming corroding accretions on the walls of the heat recovery boiler. Formation of dust build-ups in the boiler need to be cleaned regularly and potential corrosion damage checked, requiring costly and unscheduled shutdowns of the flash smelting process. Compounds of copper and zinc among other elements having high vapour pressures may volatilize during the smelting of the copper concentrate, forming dust when the process gas cools down. Also, particles of solid or liquid iron oxides originating from the ore get transported with process gas to the heat recovery boiler as a result of entrainment in the flue gas (Miettinen, 2008)
The dust deposit build-ups on the boiler walls are formed partly by direct impact of particles and partly by vapour condensation on the boiler walls. The initial deposition takes place by the condensation of vapours that contain zinc, lead, arsenic and other metals having high vapour pressures. Also, low melting point eutectic components of alkali salts such as chlorides and sulphates can act as sticky cohesive particles attaching to the boiler walls. The fine particles landing on the surface of the porous dust deposit layer react in the SO2-rich atmosphere of the boiler to sulphates. The process gas within the boiler contains SO2, O2, SO3, H2O and N2 that diffuse into the porous accretions to form a stagnant gas layer within the dust deposit structure. The composition of this gas layer may differ greatly from the composition of the process gas that is flowing on the surface of the accretion layer. Locally HCl and H2SO4 are formed and even a reducing atmosphere may exist within the dust deposit layer, allowing new reactions to take place. The local micro-atmosphere may enable metal sulphates to be reduced to secondary sulphides and even metallic components. Within the accretion layer, components may be formed that would not be stable in the gas atmosphere inside the boiler (Miettinen, 2008). This may be the mechanism by which for instance chlorides of Cu, Fe and Zn are formed within the deposit layer.
