Carolina Pettersson

Environmental risk of particulate and soluble platinum group elements released from gasoline and diesel engine catalytic converters

A comparison of platinum-group element (PGE) emission between gasoline and diesel engine catalytic converters is reported within this work. Whole raw exhaust fumes from four catalysts of three different types were examined during their useful lifetime, from fresh to 80,000 km. Two were gasoline engine catalysts (Pt-Pd-Rh and Pd-Rh), while the other two were diesel engine catalysts (Pt). Samples were collected following the 91441 EUDC driving cycle for light-duty vehicle testing, and the sample collection device used allowed differentiation between the particulate and soluble fractions, the latter being the most relevant from an environmental point of view. Analyses were performed by inductively coupled plasma-mass spectrometry (ICP-MS) (quadrupole and high resolution), and special attention was paid to the control of spectral interference, especially in the case of Pd and Rh. The results obtained show that, for fresh catalysts, the release of particulate PGE through car exhaust fumes does not follow any particular trend, with a wide range (one-two orders of magnitude) for the content of noble metals emitted. The samples collected from 30,000-80,000 km present a more homogeneous PGE release for all catalysts studied. A decrease of approximately one order of magnitude is observed with respect to the release from fresh catalysts, except in the case of the diesel engine catalyst, for which PGE emission continued to be higher than in the case of gasoline engines. The fraction of soluble PGE was found to represent less than 10% of the total amount released from fresh catalysts. For aged catalysts, the figures are significantly higher, especially for Pd and Rh. Particulate PGE can be considered as virtually biologically inert, while soluble PGE forms can represent an environmental risk due to their bioavailability, which leads them to accumulate in the environment.

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).

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.

Microstructural investigation of the KCl-induced corrosion of the austenitic alloy Sanicro 28 (35Fe27Cr31Ni) at 600°C

Abstract High-temperature corrosion of stainless steel is important, particularly in bio-fuelled boiler applications. The flue gas is rich in water vapour and alkali salts, which accelerate the corrosion of the boiler material. The focus of this paper is on the breakdown of the protective oxide scale formed on Sanicro 28, which is a highly alloyed austenitic stainless steel (35Fe27Cr31Ni), in the presence of KCl(s). Laboratory exposures were carried out at 600°C in 5% O2+40% H2O for 1, 24 and 168 hours. The samples were coated with 0.10 mg/cm2 KCl prior to exposure and uncoated samples were exposed for reference. The aim was to link the observed mass gains and microstructure to oxidation mechanisms. The oxidized samples were analyzed by XRD, SEM/EDX, FIB and TEM/EDX. The exposures results in a very complex corrosion chemistry, including, e.g. the formation of potassium chromate and the rapid transport of iron species on the surface resulting in accumulation of oxide on the former KCl particles. However, the consumption of chromium and the presence of chloride on the surface does not result in the breakdown of the protective oxide. The ability of the alloy to withstand this harsh environment is tentatively attributed to the high Cr/Fe ratio.

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.

Corrosivity of KCl(g) at Temperatures above Its Dew Point - Initial Stages of the High Temperature Corrosion of Alloy Sanicro 28 at 600°C

The influence of gaseous KCl on the high temperature oxidation of alloy Sanicro 28 (27Cr31Ni) at 600°C in 5% O2 (N2 in balance) is reported. The samples were exposed isothermally in flowing gas, the dew point of KCl being 590°C corresponding to a partial pressure of KCl of about 2·10-6 atm. The exposure time was 24, 72 and 168 hours. The samples were investigated by gravimetry, grazing incidence XRD, SEM/EDX and AES. The results show that the oxidation of Sanicro 28 at 600°C is accelerated by KCl(g) at metal temperatures above the dew point of the salt. KCl(g) reacts with the protective chromium rich oxide ((Fe1-xCrx)2O3) forming K2CrO4. The resulting chromium depletion of the oxide gives an increasing oxidation rate but does not trigger “breakaway” corrosion. The distribution of potassium chromate on the sample surface is strongly flow-dependent, showing that the rate of formation of potassium chromate is limited by the rate of transport of KCl(g) to the surface. No evidence for chlorine was found on the corroded samples by AES profiling or EDX.