What is fluidised bed agglomeration? A Combustion File downloaded from the IFRF Online Combustion Handbook ISSN 1607-9116 Combustion File No: 50 Version No: 1 Date: 23-06-2003 Author(s): Jenő Kovács Source(s): See CF Sub-editor: Neil Fricker Referee(s): Mikko Hupa Status: Published Sponsor: EuroFlam 1. Bed agglomeration Bed agglomeration problems in fluidised-bed conversion (fluidised bed combustion or gasification) are related to a high content of alkali metals in the fuel. Combined with high contents of sulphur (in combustion), chlorine, silica (from the fuel or the bed material) and phosphorus, low-melting compounds or low-melting mixtures of several compounds, so called eutectics, are formed, which become deposited on the bed particles, coating them with a sticky ash layer acting as to glue particles together. The particles may form large agglomerates, which decrease the mixing of the bed and may result in collapse of the fluidised bed, i.e. defluidisation. Bed agglomeration in fluidised-bed conversion of biomass is related to a high content of potassium. Growing plants selectively concentrate potassium, which along with nitrogen and phosphorous are the key nutrients for plant growth. Therefore potassium is rather concentrated in fast growing (annual) plants. Likely problematic fuels are: residues of agricultural crops, young energy crops or other biomass containing young organic material. 2. Mechanism of bed agglomeration There are three sintering mechanisms relevant in bed agglomeration: 1) Partial melting: sintering in the presence of a reactive non-viscous liquid phase consisting of molten alkali salts, where the solid phase is partly soluble in the liquid at the sintering temperature. The high alkali content of fuel combined with sulphur and/or chlorine form low-melting eutectics even below 700oC. 2) Viscous flow sintering or vitrification: sintering due to viscous flow of a vitreous silicate phase. When silica is heated to the melting temperature range, a highly viscous liquid phase forms. Due to its high viscosity, the liquid remains viscous on rapid cooling below the melting temperature range, forming a glassy phase; this glassy phase has a viscosity low enough to cause sintering of particles at temperatures as low as 700 to 800oC. 3) Chemical reaction: sintering due to reaction between the particles or the particles and the gas, to form a new compound binding the particles together. This mechanism is reported to be dominant in sintering of ashes rich in calcium. CaO in a gas with high CO2 partial pressure gives particle-to-particle bonding via CaCO3 formation at temperatures between 600oC and 800oC. Above 800oC these decompose to CaO and CO2. CaO in high SO2 concentration environment form CaSO4 crystals, resulting in similar sintering; however at temperature over 500oC. The main influencing factors are: concentration of potassium, chlorine, sulphur, silica, type of bed material (silica (SiO2), alumina (Al2O3), mullite (Al2O3.SiO2)), fluidisation conditions, bed and fuel particle size, temperature and ash recirculation from cyclones. 3. Result of bed-agglomeration: Defluidisation Defluidisation is indicated by a sudden decrease of the pressure drop over the bed to a low level. The pressure drop declines slowly before defluidisation, suggesting a segregation of large agglomerates in the bottom of the bed. The temperature profile inside the bed can be an indicator of defluidisation. When the bed is in its normal fluidization state, the bed temperature is very uniform. A difference in temperature between the bottom and the center of the bed is indicative of poor mixing caused by large agglomerates. In bubbling beds (relatively low fluidisation velocity), defluidisation may be due to: a) Agglomerates disturbing the good mixing and causing hot spots, aggravating agglomeration and; b) Increased particle size and inter-particle force due to the sticky coating, increasing the minimum fluidisation velocity. In circulating fluidised bed, where the velocity is much higher, agglomerates are expected at the relatively relaxed areas as in the stand pipe, non-mechanical valve, blocking the recirculating system. 4. How to predict agglomeration? Laboratory methods for assessing the slagging, fouling and agglomeration are difficult to apply since the ash produced in a laboratory environment is significantly different from the ash formed in an industrial environment. However, together with large-scale tests and mathematical modelling, the following methods and measures may give better understanding of the mechanisms: 1) Fuel analysis: a. Slagging index, fouling index b. Reactive alkali and chlorine content 2) Ash melting, sintering and agglomeration temperatures analysis: a. Standard ASTM ash fusion test b. Empirical correlations between standard ash fusion temperatures and the ash chemical composition c. Differential thermal analysis, Thermogravimetric analysis d. Electrical resistance and shrinkage method e. Laboratory sintering method (pressure strength measurement of heattreated ash pellets) f. Heat treatment mixtures of laboratory-ash and bed material and other similar agglomeration tests g. Flow properties of heat treated ash The question of how to prevent agglomeration in fluidised beds is treated in CF191. Glossary terms Agglomerate - A cluster of individual particles in which the particles are held together by surface forces resulting from a change of environment. Opposite of agglomeration is dispersion. Ash - Ash is the non-combustible material that is contained by a liquid or solid fuel, which is left as a residue after the completion of the combustion process. (See also Flyash) Bed agglomeration - The process when separate bed particles adhere to each other to form larger particles. Biomass - Biomass comprises all growing organic matter, such as plants, trees, grasses, and algae. Biomass is renewable fuel from organic origin, residues from forestry, agriculture and energy crops. Differential thermal analysis - A method used in the analysis of phase changes and the heat involved in the change, in which the temperature difference between a test sample and an inert reference sample is recorded in a uniform heating process. Energy crops - Crops grown specifically for their fuel value. These include food crops such as corn and sugarcane, and non-food crops such as poplar trees and switchgrass. Eutectic – A mixture of substances having the lowest freezing point of all possible mixtures of the substances. Fluidised bed combustion - Combustion based on the fluidisation technology. Fouling index - An index, which can be calculated from the ash analysis and which, gives an indication of the propensity for that coal to cause fouling problems during combustion. Sintering - The process in which fine particles initially touching each other become attached to each other due to a temperature that is sufficient for atomic diffusion. Slagging index - An index which can be calculated from the ash analysis and which gives an indication of the propensity for that coal to cause slagging problems during combustion. Thermogravimetric analysis - Instrumental technique that measures the weight of a sample and how this weight diminishes as the sample reacts. The sample temperature is controlled. Vitrification – Formation of a glass (a viscous silicate melt that does not crystallize when cooled to lower temperatures). Keywords Agglomerates; agglomeration; alkali; ash; bed material; biomass; defluidisation; energy crops; fluidised bed combustors; melting; potassium; silica; sintering Related Combustion Files CF 85 – What are the main fluidised bed combustion phenomena? CF 191 – How do I prevent agglomeration in fluidised beds? Sources [1] A. van der Drift and A. Olsen: Conversion of biomass, Prediction and Solution Methods for Ash Agglomeration and Related Problems. Final Report, Non-Nuclear Energy Programme Joule 3 by European Commission, contract JOR3-95-0079. [2] W. Lin and K. Dam-Johansen: Agglomeration in Fluidized Bed Combustion of Biomass Mechanisms and Co-Firing with Coal, Proceedings of the 15th International Conference on Fluidized Bed Combustion May 16 - 19, 1999 Savannah, Georgia Acknowledgements Acknowledgement is due to Mr. Bram van der Drift, ECN Biomass, for his help in literature research. File Placing [Burners]; [Fluidised Beds]; [General] Access Domain [Members’ Domain] Parity between this pdf and the present html version of this Combustion File The information contained in this pdf Combustion File edition is derived from html edition of the same number and version, as published in the IFRF Combustion Handbook (http://www.handbook.ifrf.net). The information published in this pdf edition, is that which was included in the original html edition and has not been updated since. For example there may have been minor corrections in the html version, of errors, which have been drawn to our attention by our readers. 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