Toxic emissions during co-combustion of biomass-waste wood-lignite blends in an industrial boiler

The objectives of this work were to study the PCDD/F emissions during the co-combustion of waste wood/coal co-combustion in an industrial boiler and to determine the relation of the toxic emissions to the fuel properties. Co-combustion experiments were performed in a 13.8 MWthermal industrial moving grate combustor. The fuels which were examined in this study included Greek lignite, natural uncontaminated wood, power poles and medium density fibers (MDFs) which were by-products of the plant production process. Fuel blends were prepared by mixing single components in various concentrations. PCDD/F emissions were collected during experimental runs and were analyzed according to standard methods. Low PCDD/F emissions were obtained during the co-combustion tests, lower than the limit value of 0.1 ng TEQ/Nm3. The lowest values were observed during the combustion of fuel blends containing MDF, possibly due to the inhibitory action of some of the N-containing MDF ingredients, such as urea. No direct correlation was found between the PCDD/F and the copper emissions, while examination of the PCDD/F homologue patterns revealed the predominance of the lower chlorinated isomers over the higher ones.     

Correlation between PCDD/F, PCB and PCBz in coal/waste combustion. Influence of various inhibitors

In the flue gas of co-combustion of solid waste and coal in a laboratory scale furnace high concentrations of polychlorinated dibenzo-p-dioxin and furans (PCDD/F), polychlorinated biphenyls (PCB) and polychlorinated benzenes (PCBz) have been detected. These toxic emissions have been reduced by the help of various inhibitors added to fuel before incineration. Knowledge of the congener pattern and homologue profiles of PCDD/F, PCB and PCBz is important to elaborate the mechanism of formation and inhibition of the toxic compounds formed during co-combustion of solid waste and coal. Principle component analysis (PCA) is used in order to find the similarity between the samples and separate them according their toxicity. By the help of the component analysis (CA) the best correlated congeners are effectively detected. Using linear regression between the independent variables and the indicator parameters various good correlated pairs between PCDD/F, PCB and PCBz have been elaborated. Generally it was found that the samples with higher toxicity show a good correlation between tetra- and pentachlorinated benzenes and tetra- and pentachlorinated dibenzo-p-furans. The best indicator parameter for PCDD/F World Health Organization toxic equivalent (WHO-TEQ) among the PCBz congeners investigated is 1,2,4,5-TCBz. This isomer is also significantly correlated with PCDD/F WHO-TEQ and with the sum of PCDD/F WHO-TEQ and PCB WHO-TEQ. However for samples with higher percentage of inhibitors the above mentioned relationship between the surrogate and WHO-TEQ disappeared. The PCB homologues and congeners show no correlation with PCBz and PCDD/F homologues and congeners.     

PCDD/F inhibition by prior addition of urea to the solid fuel in laboratory experiments and results statistical evaluation

The objectives of this work were to study the effect of urea addition to the fuel before the combustion on the suppression of PCDD/F emissions, to examine the influence of urea to PCDD/F isomer patterns by employing statistical analysis techniques and to determine the most effective method of urea addition. Urea in the form of powder and as an aqueous solution was mixed with RDF and the fuel mixtures were incinerated in a lab-scale reactor at 1000 degrees C. PCDD/F emitted during combustion experiments were collected in a quartz wool filter downstream the reactor unit. Analysis and quantification of PCDD/F showed that urea significantly affected PCDD/F emissions. Combustion of RDF containing 10% w/w urea resulted in PCDD/F emissions lower than 8 I-TEQ ng/g RDF, while the corresponding average value from single RDF combustion was 17 I-TEQ ng/g RDF. The PCDD/F prevention capacity of urea was independent from the method of urea addition to the fuel, as similar results were obtained after the addition of urea in the solid and in the aqueous phases. Results assessment by statistical methods showed that isomer patterns remained almost stable and were not affected by the method of urea addition.     

Formation of PCDD/PCDF

One option of recycling used contaminated packaging is to recover its high energy content. This can be performed in a normal multi-fuel power plant by co-combustion of packaging-derived fuel (PDF) or refuse-derived fuel (RDF) with fossil fuels, such as coal or peat. This work includes the results of 17 co-combustion tests and an evaluation of the results by the Principal Component Analysis (PCA) and the Partial Least Squares Projections to Latent Structures (PLS). PCA and PLS calculations showed that especially Pb, but also Cr, and Cu correlated with lower chlorinated furans (PCDFs) in the fly ash. Correlation between Sn and lower chlorinated dioxins (PCDDs) in the fly ash was also noticed. CO and PAH emission in the flue gas correlated with total PCDD/Fs in the flue gas. In a real full-scale combustion process, a single parameter in fuel, flue gas or a combustion parameter did not provide a guide to PCDD/F formation or to a level of the total PCDD/F emission, but correlations between different parameters and PCDD/Fs could be found. Although PDFs and RDF had catalytic heavy metals and chlorine, the co-combustion results showed that they can be co-combusted with peat and coal in a fluidized-bed boiler at least up to 26 % with very low total PCDD and PCDF emissions.     

Effect of liquid inhibitors on PCDD/F formation. Prediction of particle-phase PCDD/F concentrations using PLS modelling with gas-phase chlorophenol concentrations as independent variables

Emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) from municipal waste incineration are currently a subject of considerable public concern because of their extreme toxicity. PCDD/F formation in incineration processes is being studied widely, but little work has been done on their inhibition. We studied the effect of two liquid inhibitors, sodium ammonium hydrogen phosphate (NAHF) and urea (H2NCONH2), on PCDD/F formation in the combustion of liquid fuel doped with copper and chlorine using a pilot-scale plant. The inhibitors were injected into the flue gas stream at a temperature of 725 degrees C, whereupon both the chlorophenol and PCDD/F concentrations decreased. Particle-phase PCDD/F concentrations in particular decreased by up to 90% with NAHF and 70% with urea, but gas phase reduction took place only with urea. The results suggest that the formation of PCDD/Fs is hindered in the particle phase at the early stages of the PCDD/F formation chain, probably even before precursors such as chlorophenols have been formed. As a consequence, particle-phase PCDD/F concentrations can be predicted by a PLS (partial least-squares) approach with the gas-phase chlorophenol concentrations as independent variables. The structure and partial charges of Cu(+)-urea complex were calculated by the HF/3-21G basis set.     

Variables affecting emissions of PCDD/Fs from uncontrolled combustion of household waste in barrels

The uncontrolled burning of household waste in barrels has recently been implicated as a major source of airborne emissions of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). A detailed, systematic study to understand the variables affecting emissions of PCDD/Fs from burn barrels was performed. The waste composition, fullness of the barrel, and the combustion conditions within the barrel all contribute significantly to determining the emissions of PCDD/Fs from burn barrels. The study found no statistically significant effect on emissions from the Cl content of waste except at high levels, which are not representative of typical household waste. At these elevated Cl concentrations, the impact of Cl on PCDD/F emissions was found to be independent of the form of the Cl (inorganic or organic). For typical burn conditions, most of the PCDD/F emissions appear to be associated with the later stages of the burn when the waste is smoldering. Polychlorinated biphenyls (PCBs) were also measured for a subset of the tests. For the nominal waste composition, the average emissions were 76.8 ng toxic equivalency units (TEQ)WHO98/kg of waste combusted, which suggests that uncontrolled burning of household waste could be a major source of airborne PCDD/Fs in the United States.     

Chlorinated dibenzodioxin and dibenzofuran emissions from waste combustion plants in the UK

The UK Department of Trade and Industry funded extensive studies into the emissions from a variety of small scale waste combustion plants. In this paper we analyse the data on polychlorinated dibenzodioxin and polychlorinated dibenzofuran (PCDD/F) emissions from these studies. We conclude that simple correlations of PCDD/F emissions against parameters such as carbon monoxide, hydrogen chloride, feedstock composition, combustion or boiler exit temperature do not provide any guide to the emission of PCDD/F. The complex interaction between the varying fuel properties and the design features of combustion equipment mean that a greater understanding of the fundamental mechanisms is required to ensure effective control of PCDD/F at a reasonable cost.     

Assessment of emissions and removal of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) at start-up periods in a hazardous waste incinerator

A study was conducted to observe the changes in polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) levels and congener profiles in the flue gas of a hazardous waste incinerator during two start-up periods. Flue gas samplings were performed simultaneously through Air Pollution Control Devices (APCDs) (including boiler outlet, electrostatic precipitator (ESP) outlet, wet scrubbers (WS) outlet, and activated carbon (AC) filter outlet) in different combustion temperatures during a planned cold (long) start-up and an unplanned warm (short) start-up. The results showed that PCDD/F concentrations could be elevated during the start-up periods up to levels 3–4 times higher than those observed in the normal operation. Especially lower combustion temperatures in the short start-ups may cause high PCDD/F concentrations in the raw flue gas. Assessment of combustion temperatures and Furans/Dioxins values indicated that surface-catalyzed de novo synthesis was the dominant pathway in the formation of PCDD/Fs in the combustion units. PCDD/F removal efficiencies of Air Pollution Control Devices suggested that formation by de novo synthesis existed in ESP also when in operation, leading to increase of gaseous phase PCDD/Fs in ESP. Particle-bound PCDD/Fs were removed mainly by ESP and WS, while gaseous phase PCDD/Fs were removed by WS, and more efficiently by AC filter.

Implications: This paper evaluates PCDD/F emissions and removal performances of APCDs (ESP, wet scrubbers, and activated carbon) during two start-up periods in an incinerator. The main implications are the following: (1) start-up periods increase PCDD/F emissions up to 2–3 times in the incinerator; (2) low combustion temperatures in start-ups cause high PCDD/F emissions in raw gas; (3) formation of PCDD/Fs by de novo synthesis occurs in ESP; (4) AC is efficient in removing gaseous PCDD/Fs, but may increase particle-bound ones; and (5) scrubbers remove both gaseous and particle-bound PCDD/Fs efficiently.     

Emissions of PCDD/F from uncontrolled, domestic waste burning

Emissions of polychlorinated dibenzodioxin and dibenzofuran (PCDD/F) result from inefficiencies of combustion processes, most typically waste combustion. Uncontrolled combustion, such as occurs during so-called "backyard burning" of domestic waste, may therefore produce optimal conditions for formation and emission of PCDD/F. However, few assessments of PCDD/F emissions are available from these sources. This work describes the first known comprehensive assessment of PCDD/F emissions from uncontrolled, domestic waste burning. Emissions were copious, but highly variable, ranging over several orders of magnitude. The potential for emissions appears to be related primarily to combustion parameters and concentrations of various gas-phase species, the latter which may be affected by changes in waste composition, waste orientation, and/or combustion conditions.     

Urea as a PCDD/F inhibitor in municipal waste incineration

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from municipal waste incineration have been widely studied because of their extensive toxicity, and many efforts have been made to restrict their emissions. Although a number of chemical compounds have been shown in laboratory-scale tests to inhibit the formation of PCDD/Fs, few have been tested in pilot- or full-scale plants. This work evaluates the effect of urea as a PCDD/F inhibitor in a pilot-scale incinerator that uses refuse-derived fuel (RDF). The decomposition of urea under the test conditions was also studied using detailed kinetic modeling. An aqueous solution of urea was injected into the flue gas stream after the furnace at approximately 730 degrees C, with varied urea concentrations and flue gas residence times used between the furnace and the sampling point. The results demonstrate that urea can successfully inhibit PCDD/F formation in waste incineration if concentrations and injection points are properly adjusted. The kinetic model showed that urea can be rapidly decomposed under appropriate flue gas conditions, indicating that in addition to the urea molecule itself, decomposition products of urea can also be responsible for the reduction of PCDD/F production during incineration.     

Urea as a PCDD/F Inhibitor in Municipal Waste Incineration

ABSTRACT

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from municipal waste incineration have been widely studied because of their extensive toxicity, and many efforts have been made to restrict their emissions. Although a number of chemical compounds have been shown in laboratory-scale tests to inhibit the formation of PCDD/Fs, few have been tested in pilot- or full-scale plants. This work evaluates the effect of urea as a PCDD/F inhibitor in a pilot-scale incinerator that uses refuse-derived fuel (RDF). The decomposition of urea under the test conditions was also studied using detailed kinetic modeling. An aqueous solution of urea was injected into the flue gas stream after the furnace at ~730 °C, with varied urea concentrations and flue gas residence times used between the furnace and the sampling point. The results demonstrate that urea can successfully inhibit PCDD/F formation in waste incineration if concentrations and injection points are properly adjusted. The kinetic model showed that urea can be rapidly decomposed under appropriate flue gas conditions, indicating that in addition to the urea molecule itself, decomposition products of urea can also be responsible for the reduction of PCDD/F production during incineration.     

In-field measurements of PCDD/F emissions from domestic heating appliances for solid fuels

Within this project the emissions into the atmosphere of polychlorinated dibenzo-p-dioxins and -furans (PCDD/F) of 30 domestic heating appliances in Austrian households were tested. The appliances were single stoves (kitchen stove, continuous burning stove and tiled stove) and central heating boilers for solid fuels up to a nominal heat input of 50 kW. A main objective of this survey was to determine the PCDD/F emissions of domestic heating units under routine conditions. Therefore, the habitual combustion conditions used by the operators were not influenced. The original fuels and lightning supports were used and the operation of the units was carried out by the householders according to their usual practice. The data obtained were used to calculate in-field PCDD/F-emission factors. Most of the appliances have shown PCDD/F emissions within a concentration range of 0.01-0.3 ng TEQ/MJ. Modern fan-assisted wood heating boilers with afterburning and units for continuously burning of wood chips and wood pellets had the lowest emissions. High emissions were caused by unsuitable heating habits such as combustion of wastes and inappropriate operation of the appliances. There were only small differences between single stoves and central heating boilers or between wood and coal-fired appliances. The emission factors calculated are higher than those cited in literature, which are mainly derived from trials on test stands under laboratory conditions.     

Effect of copper chloride on the emissions of PCDD/Fs and PAHs from PVC combustion

The influences of temperature, air flow and the amount of copper chloride upon the types and amount of the toxic emissions such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) during combustion of polyvinyl chloride (PVC) were investigated. The mechanism concerning the effect of temperature and copper chloride on the PCDD/Fs and PAHs formation was discussed. The results shown that without copper chloride, trace amounts of PCDD/Fs and large amounts of PAHs were found in the emissions from the pure PVC combustion under various combustion conditions. The addition of copper chloride enhanced PCDD/Fs formation, but it seems that the formation of PAHs decreased with increasing amount of copper chloride, and greater total amount of PAHs were produced at the higher temperature under our experimental conditions.     

Post-combustion syntheses of PCDD/F and PBDD/F from halogen-rich fuel is suppressed by a pebble heater technology

GOAL, SCOPE AND BACKGROUND: Changes in German and European legislation shifted processing of polymer-rich shredding residues (SR) from landfill to thermal treatment. However, when waste of electric and electronic equipment (WEEE) is the source of SR, thermal treatment is complicated by halogens as well as the presence of polybrominated dioxins and furans (PBDD/F) and brominated flame retardants (BFR). Hence, WEEE requires high temperature incineration with sufficient residence times. Post-combustion synthesis of polyhalogenated dioxins and furans (PXDD/F) is dominant in the temperature range between 250-450 degrees C. Thus, a very rapid gas cooling from 450 degrees to 250 degrees C is important for proper raw gas treatment. The pebble heater technology developed by ATZ Entwicklungszentrum (Sulzbach-Rosenberg, Germany) might serve as an alternative to the state-of-the-art quench cooling. It is based on the application of a pebble bed of natural bulk material, which the exhaust gases flows through radially. It provides an excellent heat transfer and a temperature gradient in the range of 1,500-2,000 K/m. The paper presents data of a pilot application of the pebble heater technology for the treatment of raw gas derived from the incineration of polymeric materials from WEEE. METHODS: A liquid fuel was chosen in order to minimise technical modifications of the plant. It was analysed for halogens by x-ray fluorescence, for brominated flame retardants by HPLC-UV/MS and for PXDD/F by GC-HRMS. Combustion gases were rapidly cooled down to temperatures below 200 degrees C and emissions of PBDD/F and PCDD/ F were estimated without further off-gas treatment. PBDD/F emissions were computed as PCDD/F toxicity equivalents applying two different calculation approaches. RESULTS AND DISCUSSION: PCDD/F emissions accounted for 0.04 ng I-TEQ/Nm3 and are in compliance with European emission limits. Calculated PBDD/F toxicity equivalents exceeded the emission limit of 0.1 ng I-TEQ/Nm3 by factors of 75 and 208 depending on the calculation approach. A mass balance of PBDD/F and PCDD/F congeners revealed an efficient elimination of more than 95% in most cases. Lower reduction rates (76% for 2,3,7,8-TeBDF and 82% for 1,2,3,7,8-PeBDF) were attributed to incomplete combustion. An intended recovery of halogens by one-stage scrubbing downstream of the pebble heater was ineffective, recovering 28% of the applied chlorine and 9% of the bromine, only. CONCLUSIONS: Our pilot incineration test indicates that the pebble heater technology can effectively suppress a post-combustion synthesis of PCDD/F and PBDD/F, resulting in low PCDD/F emission levels without further off-gas treatment. The presented data state that WEEE is sensible to incomplete combustion, which will lead to increased PBDD/F emissions without increasing PCDD/F emission limits. This finding is especially relevant for small and low-technical incineration appliances, which have been reported to treat WEEE in developing countries and are considered to serve as a significant source of PXDD/F these days. RECOMMENDATIONS AND PERSPECTIVES: Monitoring of PCDD/F emissions only might considerably underestimate the total emission of dioxins and dioxin-like compounds. It is therefore an ineffective means for assessing resulting health risks, at least for those waste treatment plants which are considered to handle the increasing amounts of PBDD/ F-containing polymers from WEEE in future. Consequently, it is recommended to initiate a screening programme for PXDD/F emissions in large scale incineration facilities which are capable of treating WEEE shredder residues.     

Influence of start-up on PCDD/F emission of incinerators

This study aims to evaluate the influence of start-up on polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) concentration in the stack flue gas of incinerators and its contributing PCDD/F emission. The PCDD/F emission of the first sample among three consecutive stack flue gas samples of five intermittent incinerators, which sampled at a stable combustion condition after start-up, is 2-3 times higher than the mean of the others. For verifying the PCDD/F characteristics of incinerators during start-up, one continuous MSWI was investigated for two years. The elevated PCDD/F emissions of the MSWI during start-up could reach 96.9 ng I-TEQN m(-3) and still maintained a high PCDD/F emission (40 times higher than the Taiwan emission limit) even 18 h after the injection of activated carbon, indicating the memory effect. Taking the MSWI for example, which consists of four incinerators, the estimated annual PCDD/F emission from normal operational conditions was 0.112 g I-TEQ. However, one start-up procedure can generate approximately 60% of the PCDD/F emissions for one whole year of normal operations. And the PCDD/F emission, which is the result of the start-ups of four incinerators, was at least two times larger than that of a whole year's normal operations, without consideration for the PCDD/F emission contributed by the long lasting memory effect.     

Prediction of dioxin/furan incinerator emissions using low-molecular-weight volatile products of incomplete combustion

Emissions of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) from incinerators and other stationary combustion sources are of environmental concern because of the toxicity of certain PCDD/F congeners. Measurement of trace levels of PCDDs/Fs in combustor emissions is not a trivial matter. Development of one or more simple, easy-to-measure, reliable indicators of stack PCDD/F concentrations not only would enable incinerator operators to economically optimize system performance with respect to PCDD/F emissions, but could also provide a potential technique for demonstrating compliance status on a more frequent basis. This paper focuses on one approach to empirically estimate PCDD/F emissions using easy-to-measure volatile organic C2 chlorinated alkene precursors coupled with flue gas cleaning parameters. Three data sets from pilot-scale incineration experiments were examined for correlations between C2 chlorinated alkenes and PCDDs/Fs. Each data set contained one or more C2 chloroalkenes that were able to account for a statistically significant fraction of the variance in PCDD/F emissions. Variations in the vinyl chloride concentrations were able to account for the variations in the PCDD/F concentrations strongly in two of the three data sets and weakly in one of the data sets.     

Modeling the atmospheric transport and deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans in North America

The atmospheric fate of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was simulated for the year 2000 in North America using a SMOKE/CMAQ-based chemical transport model that was modified for this purpose. The 1999 USEPA emission inventories of PCDD/Fs and criteria pollutants were used. The 1995 Canadian emission inventory of criteria pollutants and the 1995 Canadian area source emissions for PCDD/Fs were used with the 2000 Canadian point source emissions. Modifications to CMAQ involved coupling it with dual organic matter (OM) absorption and black carbon (BC) adsorption models to calculate PCDD/F gas–particle partitioning. The model satisfactorily reproduced the particle bound fractions at all rural sites for which there were measured data and across the whole domain, the modeled vs. measured differences in particle bound fractions were less than 20% for nearly all congeners. The model predicted ambient air PCDD/F concentrations were also consistent with measurements. Simulated deposition fluxes were within 58% of direct measurements. PCDD/F atmospheric depositions to each of the Great Lakes were estimated for the year 2000. The results indicate that approximately 76% of the total deposition of PCDD/Fs to the Great Lakes (in W-TEQ, or toxic equivalent units as defined by the World Health Organization) is attributed to PCDD/Fs absorbed into OM in aerosol. For all of the lakes, more than 92% of all deposition is particle phase wet deposition and only 5–8% is particle phase dry deposition. Wet deposition from the gas phase is negligible. Of the 17 toxic PCDD/F congeners, the Cl_4–5DD/F compounds contribute approximately 70% to the total atmospheric deposition to the Great Lakes. The seasonal changes in the PCDD/F deposition flux track variations in ambient temperature.     

Thermal exploitation of wastes with lignite for energy production

The thermal exploitation of wastewood with Greek lignite was investigated by performing tests in a laboratory-scale fluidized bed reactor, a 1-MW(th) semi-industrial circulating fluidized bed combustor, and an industrial boiler. Blends of natural wood, demolition wood, railroad sleepers, medium-density fiberboard residues, and power poles with lignite were used, and the co-combustion efficiency and the effect of wastewood addition on the emitted pollutants were investigated. Carbon monoxide, sulfur dioxide, and oxides of nitrogen emissions were continuously monitored, and, during the industrial-scale tests, the toxic emissions (polychlorinated dibenzodioxins and dibenzofurans and heavy metals) were determined. Ash samples were analyzed for heavy metals in an inductively coupled plasma-atomic emission spectroscopy spectrophotometer. Problems were observed during the preparation of wastewood, because species embedded with different compounds, such as railway sleepers and demolition wood, were not easily treated. All wastewood blends were proven good fuels; co-combustion proceeded smoothly and homogeneous temperature and pressure profiles were obtained. Although some fluctuations were observed, low emissions of gaseous pollutants were obtained for all fuel blends. The metal element emissions (in the flue gases and the solid residues) were lower than the legislative limits. Therefore, wastewood co-combustion with lignite can be realized, provided that the fuel handling and preparation can be practically performed in large-scale installations.     

The role of bio-mechanical treatments of waste in the dioxin emission inventories

PCDD/Fs are one of the most studied molecules in the world because of their toxicity. In the last years the toxicity of these compounds has been analyzed in details. For years PCDD/F inventories have pointed out the significant role of municipal solid waste (MSW) incinerators in the overall balance. Recently, thanks to new regulations on PCDD/F emissions, in a few countries this scenario is changing: it can be demonstrated that modern MSW incinerators can play a secondary role even if the percentage of MSW sent to combustion has increased. In the latest inventories an unconventional source of PCDD/F has appeared: in nineties some biogas characterizations have demonstrated that there is a release of PCDD/F from MSW sanitary landfills. In addition, the combustion of collected biogas can generate not negligible amounts of PCDD/F. A new question can be put: does the MSW contribute with other management options to the overall balance of PCDD/F? The present work points out that a detailed inventory should take into account also the PCDD/F release from bio-mechanical treatment plants (both composting and bio-drying/bio-stabilization plants). However the contribution from this option is secondary when it is compared with the one from old MSW incinerators.     

Thermodynamic analysis and kinetic modelling of dioxin formation and emissions from power boilers firing salt-laden hog fuel

Both organic chlorine (e.g. PVC) and inorganic chlorides (e.g. NaCl) can be significant chlorine sources for dioxin and furan (PCDD/F) formation in combustion processes. This paper presents a thermodynamic analysis of high temperature salt chemistry. Its influence on PCDD/F formation in power boilers burning salt-laden wood waste is examined through the relationships between Cl2, HCl, NaCl(g) and NaCl(c). These analyses show that while HCl is a product of combustion of PVC-laden municipal solid waste, NaCl can be converted to HCl in hog fuel boilers by reactions with SO2 or alumino-silicate materials. Cl2 is a strong chlorinating agent for PCDD/F formation. HCl can be oxidized to Cl2 by O2, and Cl2 can be reduced back to HCl by SO2. The presence of sulphur at low concentrations thus enhances PCDD/F formation by increasing HCl concentrations. At high concentrations, sulphur inhibits de novo formation of PCDD/Fs through Cl2 reduction by excess SO2. The effect of NH3, CO and NOx on PCDD/F formation is also discussed. A semi-empirical kinetic model is proposed. This model considers both precursor and de novo formation mechanisms. A simplified version is used as a stack emission model. The kinetic model indicates that stack dioxin emissions will increase linearly with decreasing electrostatic precipitator (ESP) efficiency and exponentially with increasing ESP temperature.