Co-combustion of biomass and waste fuels in a fluidised bed boiler : fuel synergism
Sammanfattning: The objective of this work was to study co-combustion of biomass and waste fuels in a circulating fluidised bed boiler and to detect synergy effects with respect to flue gas composition and ash formation during boiler operation. It was also the aim to perform supplementary thermodynamic equilibrium calculations in order to support the experimental results. The base fuel used was either wood or bark pellets and the additional fuels included municipal sewage sludge, sludge from the pulp and paper industry and demolition wood. In some of the tests, additives were supplied to the boiler to enhance any effects from substances of special interest. Examples of such additives are zinc oxide, PVC, ammonium sulphate, kaolin and zeolites. The 12 MWth circulating fluidised bed boiler situated at Chalmers University of Technology was central to the investigation. All combustion tests were performed in this boiler and it provided operating data, flue gas composition and samples of fuel, ash and deposits under required combustion conditions. Great effort was put into the analyses of ashes and deposits and in excess of conventional techniques, time-of-flight secondary ion mass spectrometer (TOF-SIMS), scanning electron microscopy energy dispersive x-ray (SEM EDX) and x-ray diffraction (XRD) were applied to several of the samples to create a more complete scan of the constituents. The thermodynamic equilibrium calculations were performed using the computer program FactSage and the module EQUILIB. The thermodynamic data was collected from the database FACT. The focus of the investigation was directed towards three main areas: sulphur capture performance by lime addition to the bed, distribution of heavy metals in ashes and flue gas, and formation of deposits on heat transfer surfaces in the convective pass and the use of municipal sewage sludge as a preventive additive. The relatively high content of phosphorus in municipal sewage sludge interferes with the sulphur capture by lime and decreases the sulphur capture performance. Phosphorus reacts with calcium, which otherwise is available for reaction with sulphur, and forms compounds such as calcium phosphates. The formation was supported by equilibrium calculations and proved by analysing the ashes with TOF-SIMS. The decreased lime efficiency must be taken into account when sulphur capture strategies are decided for the reduction of SO2 emissions from co-combustion of municipal sewage sludge. Further, the use of bark pellets as base fuel during co-combustion with sulphur containing wastes reduces the sulphur emissions due to their relatively high content of calcium and potassium in connection with its low content of sulphur. The supply of heavy metals to the combustion increases dramatically when wood is replaced by municipal sewage sludge under otherwise constant conditions. The heavy metals are to a large extent recovered in the ash and captured by the flue gas cleaning system. Even the most volatile species, such as mercury, are captured and enriched in the fine fly ash. The effective metal capture is partly due to the sludge ash and partly to the bag filter. The amount of ash in the boiler increases with the sludge and the fine fly ash fraction constitutes a high particle surface area which enhances the capture of volatile metals. Further, the ash contains large amounts of several elements known to retain trace elements such as aluminium, calcium, carbon and silicon. Especially the presence of zeolites in the sludge is likely to contribute to the capture of mercury. Further, the enrichment ratios of metals in the filter ash indicate the necessity of including bag-filters in the flue gas cleaning system in order to achieve sufficient removal of toxic heavy metals. Zinc, and its effect on deposit formation, was given special attention since the metal is commonly present in demolition wood. The result showed that combustion of demolition wood contaminated with zinc alone generates only a modest amount of deposits. Demolition wood contaminated with both zinc and chlorine gives rise to more severe deposit formation. The main reason for this is the formation of alkali chlorides but also zinc chlorides in the flue gas. The formation of zinc chlorides is, under reducing conditions, thermodynamically favoured between 450 and 850°C. Under oxidising conditions, the formation is initiated at 400°C and gradually increased with the temperature. Municipal sewage sludge is not only a waste that must be disposed of, it can also be regarded as an additive to prevent deposit formation during combustion of high alkali biomass. The sludge reduces the concentration of KCl in the flue gas, impedes the deposit formation and eliminates the content of chlorine in the deposits. The occurrence is clear of though the fuel is contaminated with chlorine. The effect is partly due to sulphation of potassium and partly to potassium sequestration by the sludge ash.
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