Einfluss von Betriebsbedingungen von Holzverbrennungs- und Müllverbrennungsanlagen auf die chemische Signatur organischer Schadstoffe in den Rauchgasen.

Der Schwerpunkt dieser Arbeit bestand in der Aufklärung der Beziehungen verschiedener chloraromatischer und aromatischer Verbindungen untereinander und in Beziehung zum I-TEQ der PCDD/F aus Rauchgas- und Feststoffproben von Hausmüll- und Holzverbrennungsanlagen. Neben der Variationsbreite wurde der Einfluss besonderer Betriebsbedingungen auf die Zusammensetzung der untersuchten Substanzklassen in den verschiedenen Matrizes untersucht. Zur Abschätzung der PCDD/F-Konzentrationen wurde der gewonnene Datensatz hinsichtlich möglicher Leitparameter analysiert. Des weiteren wurden Untersuchungen zum Bildungsmechanismus der Chloraromaten und aromatischen Verbindungen durchgeführt

PCDD/F and other micropollutants in MSWI crude gas and ashes during plant start-up and shut-down processes.

Nonstationary combustion conditions at municipal solid waste incineration (MSWI) plants cause increased crude gas concentrations of polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), and other products of incomplete combustion (PIC). Such transient conditions occur, e.g., during and after start-up processes in MSWI plants. The start-up and shut-down processes of a MSWI plant were investigated in detail. PCDD/F and other PIC concentrations were determined in the crude gas, in the boiler ash, and in the ash from the electrostatic precipitator (ESP ash), with the outcome that only the start-up procedure significantly affected the concentrations of the organic pollutants in the flue gas and in the ESP ash. The shut-down procedure was evaluated as less problematic for the concentration of the organic pollutants. Moreover the concentration of the PCDD/F and other PIC in the boiler ash was determined as not influenced by shut-down and start-up processes. The homologue profiles and the congener patterns as well as the PCDF/PCDD ratio in the flue gas and in the ESP ash change during MSWI start-up. The changing patterns point at a transition from dominant de novo synthesis to precursor synthesis

Experimental and statistical determination of indicator parameters for the evaluation of fly ash and boiler ash PCDD/PCDF concentration from municipal solid waste incinerators.

On-line detectable indicator parameters in the flue gas of municipal solid waste incinerators (MSWI) such as chlorinated benzenes (PCBz) are well known surrogate compounds for gas-phase PCDD/PCDF concentration. In the here presented work derivation of indicators is broadened to the detection of fly and boiler ash fractions with increased PCDD/PCDF content. Subsequently these fractions could be subject to further treatment such as recirculation in the combustion chamber to destroy their PCDD/PCDF and other organic pollutants’ content. Aim of this work was to detect suitable on-line detectable indicator parameters in the gas phase, which are well correlated to PCDD/PCDF concentration in the solid residues. For this, solid residues and gas-phase samples were taken at three MSWI plants in Bavaria. Analysis of the ash content from different plants yielded a broad variation range of PCDD/PCDF concentrations especially after disturbed combustion conditions. Even during normal operation conditions significantly increased PCDD/PCDF concentrations may occur after unanticipated disturbances. previous termStatisticalnext term evaluation of gas phase and ash measurements was carried out by means of principal component analysis, uni- and multivariate correlation analysis. Surprisingly, well known indicators for gas-phase PCDD/PCDF concentration such as polychlorinated benzenes and phenols proved to be insufficiently correlated to PCDD/PCDF content of the solid residues. Moreover, no single parameter alone was found appropriate to describe the PCDD/PCDF content of fly and boiler ashes. On the other hand, multivariate fitting of three or four parameters yielded convenient correlation coefficients of at least r = 0.8 for every investigated case. Thereby, comprehension of plant operation parameters such as temperatures and air flow alongside concentrations of inorganic compounds in the gas phase (HCl, CO, SO2, NOx) gave the best results. However, the suitable set of parameters suited best for estimation of PCDD/PCDF concentration in solid residues has to be derived anew for each individual plant and type of ash

Changes in PCDD/PCDF formation processes during instationary phases of combustor operation - Exemplified by the use of Cl4DD isomer patterns.

In this paper results of various measurement campaigns at different municipal waste incineration (MWI) plants concerning the change of the PCDD/PCDF isomer distribution in the crude gas during transiently impaired combustion conditions are presented. The focus is on the Cl4DD isomer distributions exemplarily for all other homologue groups to demonstrate the changein PCDD/PCDF formation mechanism at transient combustion conditions. Additionally to crude gas samples, at one plant filter and boiler ash were investigated simultaneously to determine if there is any difference in the isomer distribution between the matrices. For the ash from an electrostatic precipitator (ESP ash), the boiler ash and the corresponding crude gas sample, nearly identical changes in the Cl4DD isomer distribution under transient combustion conditions in relation to the normal operation process could be detected. By comparing the Cl4DD isomer distributions from different incineration plants (two municipal waste incinerators and one little incinerator burning wood chips for heating domestic household) under transient combustion conditions, in all cases the 1,3,6,8- and 1,3,7,9-Cl4DD were dominating the isomer distribution, whereas under normal operation other isomers were predominant. Obviously PCDD/PCDF formation mechanisms under transient combustion conditions are independent from the type of incinerator and of the burned fuel, respectively.Data sets were analyzed with respect to the possible reaction mechanism via chlorophenols and a good correlation of 2,4,6-trichlorophenol during the second phase of a start-up process and during a CO experiment was found.To get more detailed information about possible formation mechanisms, at one plant the dependence of the PCDD/PCDF isomer distribution on the different matrices was studied. Separate analysis of fly ash collected at the boiler exit, subsequent gas phase, ESP ash and boiler ash under normal operation conditions showed that, apart from the fly ash, the Cl4DD isomer distributions are nearly the same in the different matrices. Surprisingly, the Cl4DD isomer distribution of the fly ash was more similar to the distributions found under transient combustion conditions