Jesper Pettersson

The influence of sulphur additions on the corrosive environment in a waste-fired CFB boiler

Corrosion/deposition field tests have been carried out in the superheater region of a commercial waste-fired 75MW CFBC boiler using air cooled probes. The influence of material temperature (450-500°C), flue gas temperature, temperature variations (i.e. thermal cycling) and additives to the fuel (elemental sulphur and dolomite) on deposition and corrosion was studied. The results presented here mainly consider the influence of sulphur additions to the fuel. The fuel was a mixture of 50% household waste and 50% industrial waste. After exposure the samples were analyzed by ESEM/EDX, XRD, AAS, FIB and IC. With no additional sulphur, alkali chlorides made up a large part of the deposit/corrosion product layer and in some cases chromate (VI) was detected. It is suggested that the chromate (VI) has formed by reaction of the protective oxide with alkali chlorides in the deposit. Adding sulphur to the fuel changed the composition of the deposits, alkali chlorides being largely replaced by alkali sulphates. No chromates(VI) were detected in the sulphur-added runs. It is suggested that adding sulphur to the fuel may decrease fireside corrosion because it changes the composition of the deposit. Alkali sulphates are much less corrosive than alkali chlorides partly because they do not form chromate(VI).

Alkali Induced Corrosion of 304-Type Austenitic Stainless Steel at 600°C; Comparison between KCl, K2CO3 and K2SO4

The influence of KCl, K2CO3 and K2SO4 on the initial stages of corrosion of 304-type (Fe18Cr10Ni) stainless steel was investigated at 600°C in 5% O2 + 40% H2O. Small amounts of salt (1.35 .mol K+/cm2) were added before exposure. The exposures were carried out in a thermobalance. Exposure time was 24 hours. Reference exposures were carried out in 5% O2 and in 5% O2 + 40% H2O. The oxidized samples were analyzed by SEM/EDX, XRD and IC. KCl and K2CO3 are very corrosive towards 304L, producing thick non-protective scales. Corrosion is initiated by the reaction of the potassium salts with the protective, chromium-rich oxide forming K2CrO4. This depletes the oxide in chromia and converts it into iron-rich non-protective oxide. In contrast, K2SO4 does not accelerate corrosion significantly.

Fireside corrosion of stainless and low alloyed steels in a waste-fired CFB boiler; The effect of adding sulphur to the fuel

Corrosion field tests have been carried out in the superheater region of a commercial waste-fired 75MW CFBC boiler using air cooled probes. Exposure time was 24 and 1000 hours. The effect of adding sulphur to the fuel on the corrosion of two high alloyed steels and a low alloyed steel was studied. The fuel consisted of 50% household waste and 50% industrial waste. The exposed samples were analyzed by ESEM/EDX and XRD. Metal loss was determined after 1000 hours. Both materials suffered significant corrosion in the absence of sulphur addition and the addition of sulphur to the fuel reduced corrosion significantly. The rapid corrosion of the high alloyed steel in the absence of sulphur addition is caused by the destruction of the chromiumcontaining protective oxide by formation of calcium chromate. Adding sulphur to the fuel inhibited chromate formation and increased the sulphate/chloride ratio in the deposit. Iron(II) chloride formed on the low alloyed steel regardless of whether sulphur was added or not.

A pilot plant study of the effect of alkali salts on initial stages of the high temperature corrosion of alloy 304L

Alloy 304L was exposed for between 15 min to 12 hr in the 12MW CFB research boiler at the Chalmers university of technology using an air-cooled probe. The base fuel consisted of a mixture of 67% wood chips and 33% pellets. In addition to the base fuel experiment, a number of exposures were performed where S and Cl was added to the fuel in the form Of SO2(g) and HCl(aq) in order to control the flue gas chemistry in the superheater region. After the exposures the samples were analysed by ESEM/EDX, XRD and SAM. Burning a mixture of woodchips/pellets without adding sulphur or chlorine results in the formation of K2SO4 deposits on the corrosion probes. When HCl is added to the fuel KCl deposits form. The simultaneous addition of HCl and SO, results in a deposit consisting of a mixture of KCl and K2SO4. In all environments studied an oxide in the 100nm range forms. With time, the oxide becomes covered by ash deposits. After exposure to the biomass flue gas environment, the oxide is enriched in K, especially the outer part. Chlorine is not present in the oxide even when the KCl(s) forms on the surface. It is suggested that potassium chromate formation occurs by the reaction of potassium chloride with chromium oxide.

KCl-Induced High Temperature Corrosion of Austenitic Stainless Steel 304L – The Influence of SO2

The effect of SO2 on the oxidation of alloy 304L in O2+H2O and O2+H2O+KCl environment has been investigated at 600°C. Exposure time was 1-168 hours. The exposed samples were analyzed by SEM/EDX, XRD and IC. In dry O2, a protective and chromium-rich corundum-type oxide forms. In the presence of H2O(g), chromium is volatilized in the form of CrO2(OH)2(g). The corresponding chromium depletion of the protective oxide triggers a partial loss of protective properties resulting in the formation of oxide islands on the alloy grain centers. The oxide islands consist of an outward growing hematite layer and an inward growing FeCrNi spinel layer. By coating the samples with KCl the chromia depletion of the protective oxide dramatically increases due to the formation of K2CrO4. This leads to breakaway corrosion, a rapidly growing scale forming all over the surface. The resulting thick scale has a similar structure as the oxide islands formed in the absence of KCl. The addition of 300 ppm SO2 to the O2+H2O and O2+H2O+KCl environments results in a drastic reduction of corrosion rate. In O2+H2O environment the effect of SO2 is attributed to the formation of a thin sulphate film on the oxide surface that impedes chromium volatilization and decreases the rate of oxygen reduction on the oxide surface. In O2+H2O+KCl environment the corrosion mitigating effect of SO2 is mainly attributed to the rapid conversion of KCl to K2SO4. In contrast to KCl, K2SO4 does not deplete the protective oxide in chromium by forming K2CrO4.

Is KCl(g) corrosive at temperatures above its dew point? - Influence of KCl(g) on initial stages of the high temperature corrosion of 11% Cr steel at 600 degrees C

The influence of gaseous KCl on the high temperature oxidation of CrMoV11 1 (X20) steel at 600degreesC is reported. The sample temperature was above the dew point of KCl, the partial pressure of KCl being about 5ppm. The samples were investigated by a number of surface analytical techniques including grazing angle XRD, SEM/EDX, and SAM. CrMoV11 1 steel shows protective behaviour in clean dry O-2 and O-2/H2O environment because of the formation of a chromium-rich oxide (alpha-(Fe,Cr)(2)O-3). It is Often considered that alkali salts accelerate the corrosion of steel only when present on the surface in solid or liquid form. In contrast, the present result shows that gaseous KCl is very corrosive, also in the absence of condensation. KCl(g) reacts with chromium in the scale, forming K2CrO4(s). This depletes the protective oxide in chromium and leads to the formation of non-protective hematite, Fe2O3.