No abstract

Gaseous HCl released during combustion is one reason for the severe materials degradation often encountered in power generation from waste and biomass. In this study, three stainless steels (the low alloyed EN 1.4982, the standard EN 1.4301 and the higher alloyed EN 1.4845) were tested by repeated thermal cycling in an environment comprising N 2 -10%O 2 -5%H 2 O-0.05%HCl at both 400 and 700°C. The materials were exposed with ground surfaces and preoxidised at 400 or 700°C. A positive effect of preoxidation is evident when alloys are exposed at 400°C. Oxide layers formed during preoxidation effectively suppress chlorine ingress for all three materials, while chlorine accumulation at the metal/oxide interface is detected for surface ground specimens. The positive effect of preoxidation is lost at 700°C and corrosion resistance is dependent on alloying level. At 700°C metal chloride evaporation contributes significantly to the material degradation. Based on the results, high temperature corrosion in chlorinating environments is discussed in general terms.

The major drawback to generating electricity from waste fired boilers is the rapid corrosion of superheaters which increases the maintenance costs. Within the last few years, it has been shown that additions of ammonium sulphate to biomass fired boilers decrease the corrosion tendencies. This paper reports on the effects of ammonium sulphate on corrosion in a waste fired CFB boiler. Air cooled probes were exposed at a position corresponding to the one of superheater tubes. The probe temperature was 500uC, corresponding to a steam temperature of y450uC. Both the austenitic steel EN1?4301 (Fe-18Cr-9Ni) and the low alloyed ferritic steel EN1?7380 (Fe-2?25Cr-1Mo) were tested. During exposure, the concentration of alkali chlorides in the flue gas was measured and a decrease was observed when adding ammonium sulphate. After 4 h of exposure, the probes were removed for detailed analysis with SEM-EDS, TOF-SIMS and XRD. The sides of the tubes facing the flue gas were covered with a calcium rich deposit, while relatively more sodium and potassium were present on the lee side. The results also show that ammonium sulphate shifted the deposit composition from chloride rich and highly corrosive, to one significantly less corrosive and dominated by sulphates of sodium, potassium and calcium. Metallography shows a marked difference in corrosion attack between the two steels. Iron chlorides accumulate at the metal/oxide interface of the ferritic steel, while the amounts of iron chlorides were significantly lower in the austenitic steel. These results indicate that ammonium sulphate has the potential to reduce corrosion in waste fired boilers and that austenitic stainless steels are more likely to resist corrosion in these environments than low alloyed ferritic steels.

Corrosion of superheater tubes is a serious problem during combustion of fuels with a high content of chlorine, such as waste and certain biomasses. The alkali chlorides are released to the flue gas and may condense on the heat exchanger tubes forming corrosive, chloride-rich deposits. In this work the effect of ammonium sulphate ((NH 4 ) 2 SO 4 ) injection on gaseous alkali chlorides, deposit chemistry and initial corrosion attack of superheater tubes during biomass combustion have been investigated. The investigation was carried out at three different sulphate injection rates (reference, low and high) and at three air excess ratios ( ¼ 1.1, 1.2 and 1.4). Short-term exposures of Sanicro 28 specimens, using temperature controlled probes, were used for deposit collection and to study the initial corrosion attack. The results showed reduced concentrations of potassium chloride in the flue gas when injecting ammonium sulphate and in particular in combination with high air excess ratios. A decrease of chlorine was also observed in the deposit, but the concentrations did not always correlate to the flue gas measurements. In particular, it was evident that a subsequent sulphation occurred on the tube surface at low air excess ratios. Metallography revealed that sulphation reactions on the tube surface, rather than in the flue gas, had a detrimental effect on the initial corrosion attack. As a consequence, the corrosion attack correlated more clearly to the KCl(g) concentration in the flue gas than the chlorine content in the deposit.

No abstract