Abstract
New advanced combined cycle coal-fired power generation systems are dependent on improvements in gas turbine technology and the development of hot gas cleaning techniques. These techniques are not only necessary to meet environmentally accepted emission limits for SOx and NOx but also to prevent downstream equipment from corrosion and erosion. Volatile alkali vapours in the exhaust gases produced by either coal gasification or combustion lead to corrosion of the gas turbine blades resulting in reduced operating life. Consequently, alkali removal systems which can operate upstream of the gas turbine have been incorporated into the development of the clean coal technologies.A number of studies on alkali removal systems have been performed in the temperature range of 800°C - 1000°C. Solid aluminosilicates, such as emathlite, activated bauxite, kaolinite and Fuller's Earth, react with alkali vapours at high temperatures and therefore have been characterised as suitable alkali sorbents. Fuller's Earth was identified as potentially the most suitable sorbent for use in the UK at the specified operating temperatures. This material was studied in detail by McLaughlin (1990) for use in a fixed bed configuration within the British Coal Air-Blown Gasification Cycle. Recently, it has been recognised that if ceramic filters are used for the removal of fine particulates, operating temperatures for alkali sorption will have to drop to 400°C-600°C, since these filters fail mechanically at higher temperatures. Much of the alkali will condense under these conditions and be removed by the filtration stages. However, the residual alkali levels may still exceed the revised turbine inlet specification of 24 ppb wt. Hence further studies of alkali sorption are required in this lower temperature region. During this work, it proved difficult to obtain accurate results at temperatures as low as 600°C, because of the low level of vapour phase alkali. However, experiments were performed successfully at 650°C and atmospheric pressure, on the fixed bed sorption rig used previously for tests at 827°C and 927°C. Tests comparing Fuller's Earth and kaolin, showed kaolin to have a higher sorption capacity at this temperature. Fixed bed tests with sodium and potassium were performed with Fuller's Earth pellets. The runs were of 200-600 hrs duration, with 4.58 ppm wt NaCl (1.8 ppm wt Na), 5 %vol H2O and up to 160 ppmv HCl in the inlet gas stream. Alkali uptake profiles were generated from chemical analysis of precise layers of pellets removed from the bed. Extensive modifications and improvements in analytical procedures enabled a closure of the mass balance of >99% to be achieved for a 600 hr run. Alkali exit levels measured using alumina wool filter pads in the exit gas were of the order of 5-6 ppb wt. Fuller's Earth pellets which had been pre-treated in gasifier gas and which were therefore contaminated with carbon, were tested and no difference was observed in their Na characteristics. Element mapping techniques based on Scanning Electron Microscopy, confirmed that a shrinking core model for Fuller's Earth grains and kaolin pellets was appropriate. The 'two-reaction' mechanism proposed by McLaughlin (1990), was used to fit the experimental results at 650°C. Albite was identified by X-ray diffraction studies as the reaction product under high-acid conditions and nepheline under non-acid conditions. Exit gas analysis studies with an on-line monitor for HCl, showed the production of HCl to be directly connected with the presence of NaCl vapour and to increase significantly with the presence of water vapour in the system. However, the detailed reaction mechanism has not been identified yet. The theoretical model developed for the high temperature studies (McLaughlin, 1990), using the pellet-grain model and the 'tank-in-series' method of solution has been applied successfully at 650°C. Parameters were extracted by curve fitting theoretical to experimental Na uptake concentration bed profiles. To test the numerical methods and the Szekely assumptions used in the McLaughlin program, two new computer programs were developed. The first, tested the pellet-grain model for a single pellet and the second was developed to solve the model more rigorously with a variable-order, variable-time-step numerical method. The new fixed bed model also incorporates the effects of temperature and pressure on selected parameters. It was used to predict the performance of a full-scale unit operating at 650°C and 24 bara. The results indicate that a bed of Fuller's Earth pellets, 3-10 mm in diameter, 4 m long and 4 m wide can achieve exit alkali levels below 20 ppb wt in continuous operation for up to 24,000 hrs.