Mercury species, mass flows and processes in a cement plant

The aim of the study was to evaluate the behaviour of mercury in the cement clinker production process. Simultaneous measurements of mercury in all important materials and gas streams were performed in three sampling periods on about 300 solid samples and about 80 samples taken from gas streams. Mercury species in flue gases at characteristic parts of the process were measured as total Hg(t), particulate Hg(p), elemental Hg⁰(g) and reactive Hg²⁺(g) mercury. Based on the results of measurements, mercury mass flows and mass balances of the whole and in certain parts of the process were evaluated. It was shown that the process comprises many mercury cycles which are strongly dependent on the operating conditions and technological specifics. Cycling of mercury causes a significant enrichment of mercury inside the process. In the annual mercury input of about 27 kg, raw materials accounted near by 60% and fuels about 40% (i.e. petrol coke 31%, waste tyres 10% and waste oil 0.4%). The annual emission of mercury represented 40-70% of the inputs, while cement clinker only contained about 10%. The difference between inputs and outputs (11-45%) obtained in the annual mass balance could be assigned to mercury recycling and significant enrichment inside the process, as well as variability between spot measurements. The parts of the process with the highest mercury mass flows and the lowest material/gas flows were identified. Such points represent an opportunity to remove a significant amount of mercury from the process at low material flows and to improve mercury control. Mercury was mainly emitted in gaseous form with 92% (direct mode) or 89% (combined mode) as Hg(g) on average, of which about 2/3 was as Hg²⁺(g), and about 1/3 as Hg⁰(g). Only a small part (the rest) was emitted as particulate Hg(p). Shares of individual mercury species in the last sampling period were 65.7% Hg²⁺(g), 34.0% Hg⁰(g) and 0.3% Hg(p) on average. Ratios between individual mercury forms were found to be related to operating modes. The quantities of Hg(t), Hg(g) and Hg²⁺(g) emitted were higher when operating with the raw mills off (direct mode). It was seen that the efficiency of Hg removal was strongly related to the dust removal efficiency. Bag filters very efficiently removed all mercury species.