Chemical kinetic modelling of PCDD formation from chlorophenol catalysed by incinerator fly ash

A kinetic model is developed for PCDD formation from chlorophenol catalysed by incinerator fly ash. The key step in the model is a Langmuir-Hinshelwood type elementary step for the coupling of two adsorbed chlorophenol species to PCDD. Kinetic expression is derived which can relate PCDD formation rates with process variables including temperature, precursor concentration, fly ash loading and number of active sites in fly ash. Calculated PCDD formation rates based on this kinetic model are in good agreement with laboratory measurements reported in the literature. When the model is applied to industrial incinerator conditions, at maximum a PCDD yield of 10(-3) microg/N m3 is calculated.     

Kinetics of carbon degradation and PCDD/PCDF formation on MSWI fly ash

The native carbon oxidation and PolyChloroDibenzo-p-Dioxins and PolyChloroDibenzoFurans, PCDD/F, formation were simultaneously studied at different temperatures (230-350 degrees C) and times (0-1440 min) in order to establish a direct correlation between the disappearance of the reagent and the formation of the products. The kinetic runs were conducted in an experimental set up where conditions were chosen to gain information on the role of fly ash deposits in cold zones of municipal solid waste incinerators in PCDD/F formation reaction. The carbon oxidation measured as the decrease of total organic carbon of fly ash was in agreement with the carbon evolved as sum of CO and CO(2). The carbon mass balance indicated an increase in the efficiency of carbon conversion in CO and CO(2) with temperature. The CO and CO(2) formation was the result of two parallel pseudo first order reactions thus giving significant information about the reaction mechanism. PCDD/F formation as a function of temperature showed that the maximum formation was achieved in a narrow range around 280 degrees C; the time effect at 280 degrees C was a progressive formation increase at least up to 900 min. The PCDF:PCDD molar ratio increased with temperature and time, and the most abundant homologues were HxCDD, HpCDD, OCDD for PCDD, and HxCDF, HpCDF within PCDF. These experimental results supported the hypothesis that the formation mechanism was the de novo synthesis.     

Influence of residual carbon on the decomposition process of PCDD/Fs in MSWI fly ash

In heating treatment of fly ash to reduce PCDD/Fs, cooling process is important to inhibit de novo formation of PCDD/Fs. In this study, assuming that residual carbon is the dominant factor of de novo synthesis, the relation between PCDD/Fs and residual carbon was examined. Firstly, by using MSWI fly ash which was treated in an actually operated facility, both the content of PCDD/Fs and residual carbon were decreased as heating temperature increased. At temperatures higher than 400 degrees C, the reduction rate of residual carbon was higher than 20% and more than 95% of PCDD/Fs was decomposed. In order to simulate a heating treatment process, fly ash was heated at different temperatures and gas atmospheres, oxygen or nitrogen. Heated fly ash was placed for 2 h at 300 degrees C in oxygen to promote de novo synthesis, or cooled immediately. As a result, good correlation between PCDD/Fs and residual carbon was found, therefore it was shown experimentally that residual carbon was the main factor for PCDD/Fs formation by de novo synthesis in fly ash.     

Characterization of residual carbon influencing on de novo synthesis of PCDD/Fs in MSWI fly ash

Using 19 samples of fly ash collected from various MSW incineration facilities, residual carbon was characterized by gasifiable fraction at 450 degrees C (C450), and the correlations with de novo synthesis of PCDD/Fs were experimentally examined. Fly ashes were classified into three groups by the ratio of C450 to total residual carbon. By comparison of CO and CO2 generation patterns with those of reference materials, unburnt carbon of solid waste and activated carbon powder injected into flue gas were identified as a carbon source in fly ash. In the experiment of de novo synthesis of PCDD/Fs, the content of PCDD/F synthesis depended on C450 regardless of the origin of carbon. In addition, the model to predict the content of PCDD/F synthesis, DeltaPCDD/F=0.989.Cu.C450, fitted well with experimental values.     

Modeling the formation of PCDD/F in solid waste incinerators

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) appear in unacceptable amounts in the gaseous emissions during the incineration of wastes containing significant quantities of chlorine and metals, such as MSW and medical waste. They are formed both in the gas phase at temperatures above 600 degrees C and on the surface of the solid phase (flyash) in the temperature range 400-225 degrees C. Both the precursor (from existing smaller chlorinated molecules) and de novo (from elemental carbon) routes are involved. An empirically derived global model for their de novo formation on flyash in MSW and medical waste incinerators has now been extended to include the precursor mechanism, and a gas phase formation component, with separate rate expressions for PCDD and PCDF. Homogeneous PCDD formation is governed by the concentration of chlorophenols and PCDF by that of chlorophenols and chlorobenzenes. The result is more complete system which distinguishes between the gas and solid phase contributions to the I-TEQ. An additional step for the adsorption of gaseous PCDD/F back onto the solid phase during cooling suggests this should be minimal in the gas ducts of an incinerator. The extended model has been tested against experimental data collected from a well-controlled pilot incinerator and commercial incinerators, and found to adequately describe the measured outputs. With the model it should be possible to predict the PCDD/F emissions from commercial incinerators, provided that the ash properties and the overall temperature-time profiles are known.     

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.     

Generation of PCDD/F in fly ash from municipal solid waste incinerators

Fly ash from municipal solid waste incinerators (MSWIs) has been characterized in terms of polychlorinated dibenzyl-p-dioxin and polychlorinated dibenzofuran (PCDD/F) content. Increasing values of PCDD/Fs have been found to correlate with decreasing temperatures of sampling points in flue gas treatment lines of the plants, confirming other researchers' findings about temperature as the major controlling parameter for the PCDD/F formation. Measured PCDD/F ratios show that de novo synthesis is the dominant formation mechanism. The increasing trends of particulate-bound PCDD/Fs can be explained not only through the dominant de novo synthesis process but also considering the adsorption of gaseous PCDD/Fs on fly ash deposits, even outside the typical de novo synthesis temperature ranges. The effective role of a post-combustor unit, imposed by Italian law to destroy PCDD/ Fs, also needs to be carefully reconsidered.     

Laboratory studies on formation and minimisation of polychlorinated dibenzodioxins and -furans (PCDD/F) in secondary aluminium process

The objectives of this work were to study the formation mechanisms of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) in thermal aluminium recycling processes by use of laboratory experiments. The pattern of isomers of PCDD/F indicates that de novo synthesis is important in aluminium smeltery. The mechanisms of PCDD/F formation in aluminium smelting are similar to that of various incineration processes of waste material. The results of bioanalysis (EROD-test) confirms the existence of de novo synthesis of PCDD/F, but points out to the existence to some additional, toxic compounds of unknown structure. To reduce the amount of PCDD/F the input of carbon at the metal should be reduced; in addition the metal smeltery plants should be cleaned from fly ash particles. It is suggested to use good primary methods in the technical plants like constant feeding of the metal into the oven will minimise PCDD/F concentration. The biological EROD-bioassay is a good tool to estimate PCDD/F-TEQ values also for this technical process simulated in the laboratory.     

Generation of PCDD/F in Fly Ash from Municipal Solid Waste Incinerators

Abstract

Fly ash from municipal solid waste incinerators (MSWIs) has been characterized in terms of polychlorinated dibenzyl-p-dioxin and polychlorinated dibenzofuran (PCDD/F) content. Increasing values of PCDD/Fs have been found to correlate with decreasing temperatures of sampling points in flue gas treatment lines of the plants, confirming other researchers’ findings about temperature as the major controlling parameter for the PCDD/F formation. Measured PCDD/F ratios show that de novo synthesis is the dominant formation mechanism. The increasing trends of particulate-bound PCDD/Fs can be explained not only through the dominant de novo synthesis process but also considering the adsorption of gaseous PCDD/Fs on fly ash deposits, even outside the typical de novo synthesis temperature ranges. The effective role of a post-combustor unit, imposed by Italian law to destroy PCDD/Fs, also needs to be carefully reconsidered.     

Matrix effects on the de novo synthesis of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes

The formation of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes in de novo synthesis experiments have been studied on model fly ashes with a wide range of matrices. The model fly ash consisted of 18 selected matrices with the addition of CuCl(2) x 2H(2)O, activated charcoal and NaCl. The studied matrices were not restricted to the commonly investigated matrices with defined chemical composition (silica gel, alumina, florisil) and industrially produced adsorbents with silicate structures (diatomaceous earths), but also included natural occurring matrices (clays, kaolin, bentonite and feldspars). In addition fly ashes from a hazardous waste incinerator were included in the study for comparison. Differences in the isomer composition (homologue profiles and isomer patterns) of the substances formed by de novo synthesis experiments are discussed in dependence on the chemical composition of the studied matrices. The de novo synthesis experiments on matrices with silicate structures resulted in high concentration of mainly perchlorinated aromatic compounds while for other matrices in particular alkaline matrices a homologue shift to lower chlorinated homologues and lower formation rates were found. The paper discusses the resulting PCDD/PCDF pattern and compares them to the PCDD/PCDF profile found in naturally occurring kaolin and ball clay (illite).     

A simple kinetic model of PCDD/F formation by de novo synthesis

A simple fixed-bed reactor model is used to describe experimental data about the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) from fly ash carbon. The heterogeneous oxidation of graphite-like carbon is represented by a reaction which is first order in carbon and one half order in oxygen. The same orders of reaction are assumed to be valid for PCDD/F formation, such that the oxidation of fly ash carbon would have three parallel channels leading to COx, PCDD and PCDF. In addition, PCDD/F degradation by oxygen is considered and appropriate rate constants were fitted to simulate the experimental data. The effects of water vapour and particulate copper on PCDD/F formation are included. As a result, an overall kinetic model of PCDD/F formation is obtained which describes most of the experimental data with reasonable accuracy. The main reaction channel, COx formation, needs to be understood more completely, in order to interpret PCDD/F reaction pathways better. The model can be extended to include other chlorinated aromatics and the gas/particle partitioning of the semivolatiles. It provides a basis for the qualitative and quantitative interpretation of fixed-bed and flow reactor results and it is hoped to be applicable to industrial installations like waste incinerators and metal smelters.     

The formation and emission of dioxins in large scale thermal processes

The paper assesses extensive data of PCDD/F measurements on flue gas emissions from thermal processes, including, e.g. municipal solid waste incinerators (MSWIs), combustors of wood and industrial waste, coal fired powerplants and boilers, ferro and non-ferro processes. Numerous investigators have conducted laboratory experiments to assess the formation mechanisms of PCDD/F. The results, obtained from fixed-bed experiments, have been critically evaluated and indicate that de novo synthesis is the dominant mechanism in actual thermal processes where conditions that favour the precursor formation are not experienced. The analysis of PCDD/F profiles from the large scale thermal processes in general, and MSWIs in particular, supports the dominant role of the de novo synthesis, irrespective of the type of thermal process considered. The PCDF/PCDD ratio exceeds 1 and the degree of chlorination points towards the dominant presence of HpCDD and OCDD within the dioxin group, and of PeCDF, HxCDF and HpCDF within the furan group. Since real-time measurement of PCDD/F is impossible, the correlation of PCDD/F emissions with operating parameters and/or emission levels of other more easily measured pollutants could be a tool in predicting the PCDD/F formation levels. Data of Flemish MSWIs were used to statistically assess such correlations. From an evaluation of the data at a given operating temperature, misleading conclusions can be drawn. Only the effect of temperature is evident. After converting all data at a reference temperature of, e.g. 230 degrees C, PCDD/F concentrations achieve nearly constant values, irrespective of the values of other parameters, thus stressing that the major controlling parameter for the PCDD/F emission is the temperature of the ESP. The PCDD/F concentrations increase with temperature in the range up to 280 degrees C. The ESP temperature should be kept preferably between 180 degrees C and 200 degrees C, where de novo synthesis is reduced and where PCDD/Fs are increasingly adsorbed on the fly ash, in line with the standard temperature dependence of adsorption isotherms.     

Effects of sulfur dioxide, hydrogen peroxide and sulfuric acid on the de novo synthesis of PCDD/F and PCB under model laboratory conditions

In a laboratory model system consisting of fly ash from municipal waste incinerator, CuCl2 x 2H2O, NaCl and activated carbon in N2 + 10% O2 atmosphere, the de novo synthetic reactions of formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) were studied under laboratory conditions in the presence of sulfur dioxide, hydrogen peroxide, and sulfuric acid. It has been found that the formation of PCDD is suppressed by sulfur dioxide more efficiently than the formation of PCDF. A similar effect has also been observed in the presence of hydrogen peroxide. The formation of PCDF is strongly suppressed in the presence of sulfuric acid. On the basis of the experimental results and thermodynamic calculations, the following mechanisms are proposed and discussed: oxidative destruction of PCDD and PCDF oxygen rings, conversion of cupric chloride and possibly also cupric oxide into the non-reactive sulfate, and the Deacon oxychlorination processes catalyzed by cupric chloride.     

Formation of polychlorinated dibenzo-p-dioxins/dibenzofurans from residual carbon on municipal solid waste incinerator fly ash using Na37Cl

Na37Cl was used to study the role of chlorine in the formation of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) from carbon. Adding Na37Cl to fly ash showed that this compound was a (relatively) poor chloride source; chlorine naturally present on the ash - which could include both chlorine in residual carbon and (metal) chlorides - was found to be ca. 17x more reactive. When both Na37Cl and CuCl2 were added to aqueous extracted fly ash, the percentage of 37Cl from Na37Cl included in PCDD/F increased, compared to the combination of Na37Cl/fly ash. When Na37Cl and CuCl2 were exchanged in water, followed by evaporation of the solvent, and mixed with aqueous extracted fly ash, the percentage of 37Cl included in PCDD/F was much higher. Apparently, direct transfer of 37Cl from CuCl2 to carbon and PCDD/F was much faster than transfer of 37Cl- from Na37Cl via a metal chloride (such as CuCl2) to carbon and PCDD/F. In addition to chlorine in PCDD/F originating from exchanged NaCl/CuCl2, chloride left on the fly ash after aqueous extraction and chlorine present in residual carbon could also have been incorporated in PCDD/F.     

Dioxins and their fingerprint in size-classified fly ash fractions from municipal solid waste incinerators in China—Mechanical grate and fluidized bed units

The distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), in brief dioxins, has seldom been addressed systematically in fly ash from municipal solid waste incinerators (MSWIs). This study shows the amount and fingerprint of PCDD/Fs in fly ash from four different Chinese MSWIs, that is, three mechanical grate units and one circulating fluidized bed unit. In these fly ash samples, dioxins-related parameters (international toxic equivalent quantity, total amount of PCDD/Fs, individual isomer classes, and 17 toxic 2,3,7,8-substituted congeners) all tend to increase with decreasing particle size for mechanical grate incinerators, yet only for the finest fraction for fluidized bed units. Moreover, the fluidized bed incinerator seems superior to grate incineration in controlling dioxins, yet a comparison is hampered by internal differences in the sample, for example, the fluidized bed fly ash has much lower carbon and chlorine contents. In addition, the presence of sulfur from mixing coal as supplemental fuel to the MSW may poison the catalytic steps in dioxins formation and thus suppress the formation of dioxins. With more residual carbon and chlorine in the fly ash, it is easier to form dioxins during cooling. Nevertheless, there is no apparent relation between Fe, Cu, and Zn contents and that of dioxins in fly ash.

Implications This paper is of interest because it presents the amounts and distribution of PCDD/Fs in fly ash samples from some typical waste incineration plants in China, featuring distinct incinerator types, combustion conditions, fuel composition, or residual carbon, chloride, and heavy metal contents in fly ash.     

Levels and characteristic homologue patterns of polychlorinated dibenzo-p-dioxins and dibenzofurans in various incinerator emissions and in air collected near an incinerator

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were monitored in stack gas and fly ash of various Korean incinerators and in air samples collected near the facilities. Concentrations of PCDD/Fs in emissions were investigated, and characteristic PCDD/F homologue patterns were classified using statistical analyses. The PCDD/F emission levels in stack gas and fly ash samples from small incinerators (SIs) were higher than those from municipal solid waste incinerators (MSWIs). The PCDD/F concentrations ranged between 0.38 and 1.16 pg I-TEQ/m3 (21.2-75.2 pg/m3) in ambient air samples. The lower-chlorinated furans were the dominant components in most of the stack gas and fly ash samples from SIs, although this was not the case for fly ash from MSWIs. This homologue pattern is consistent with other studies reporting a high fraction of lower-chlorinated furans in most environmental samples affected by incinerator emissions, and it can be used as an indicator to assess the impact of such facilities on the surrounding environment.     

Correlation of polychlorinated naphthalenes with polychlorinated dibenzofurans formed from waste incineration

Isomer composition of polychlorinated naphthalenes (PCNs) was measured for municipal waste incinerator fly ash samples and for emission samples produced from soot and copper-deposit experiments conducted at the United States Environmental Protection Agency (US-EPA). Two types of PCN isomer patterns were identified. One pattern contained specific PCN isomers in which chlorine atoms are substituted as if the peri(alpha-) position were dechlorinated from the higher chlorinated PCNs one by one. In another pattern, the isomers had a tendency for the chlorine atoms to assume successive positions on the naphthalene ring, which may be caused by specifically oriented chlorination. Some of these isomers increased, together with several polychlorinated dibenzofuran (PCDF) and a few polychlorinated dibenzo-p-dioxin (PCDD) isomers. The ratios between some specific PCN, PCDF, and PCDD isomers measured for the fly ash samples agree with those obtained from the soot and copper-deposit experiments. The observations suggest that these isomers were formed possibly from de novo synthesis utilizing the carbon structure contained in soot under the catalytic effect of a copper compound. Typical isomers for PCNs and PCDFs produced from incineration emissions were identified.     

Adsorption of PCDD/F on MWI fly ash

The removal of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) from waste incinerator off-gas is a costly task, because a considerable part of the PCDD/F may exist in the gas phase (often 50-100% around 200 degrees C). The volatile fraction passes the particle filter and the subsequent gas cleaning equipment, so that an additional unit is needed to remove the gaseous PCDD/F from the flue gas. Moreover, dioxins and furans can accumulate in some parts of the equipment in a way that they can act as a latent source. In this work, we investigate the possibility to adsorb the PCDD/F at the fly ash particles and to remove them during the filtration. The gas/particle partitioning of the PCDD/F depends on the temperature, the vapor pressure, the particle size, the particle number density and on the physical and chemical properties of the particle surface. These relationships are investigated by model calculations and by pilot scale experiments (500 Nm3/h) which employ one selected hexachlorinated dioxin congener. At room temperature, approx. 90% of the HxCDD are found in the particulate phase, while at 135 degrees C that portion is only 10%. This means that at ambient temperatures, the gas/particle partitioning of the dioxin corresponds well to the sublimation equilibrium. At higher temperatures, it is much different from the sublimation equilibrium and the apparent adsorption enthalpy is smaller than the enthalpy of sublimation. This observation is in agreement with literature data. From the above experiments and from similar literature data, the efficiency of fly ash particles as a sink for PCDD/F can be evaluated. The data suggest that the adsorption rate is not the limiting factor for the transfer into the particulate phase. The important factors appear to be the chemical composition of the fly ash and the temperature.     

Influence of temperature on PCDD/PCDF desorption from waste incineration flyash under nitrogen

A municipal solid waste incinerator flyash was heated to between 200 and 400 degrees C under nitrogen in a bench-scale, static bed reactor for 4 days soak time. The influence of temperature on the levels of PCDD and PCDF remaining in and desorbed from the ash were investigated using GC-MS/MS. PCDD and especially PCDF formation was seen on the flyash between 225 and 300 degrees C. Large increases in the I-TEQ of the treated ash relative to the increase in its overall PCDD/PCDF content indicated that the formation of 2378-substituted congeners was favoured over that of other substitution patterns. In the absence of a source of gaseous oxygen, formation was mainly attributed to de novo reactions involving solid phase oxygen. Dechlorination of the PCDD/PCDF in flyash became increasingly important above 275 degrees C. Maximum desorption was seen at 325 degrees C, with the equivalent of 35 wt% of the PCDD/F in the original flyash being recovered from the exhaust traps at this temperature. The desorbed species were mainly M(1)CDD/CDDF-T(3)CDD/CDDF resulting from dechlorination of higher chlorinated PCDD/PCDF, with consequently low I-TEQ values.     

Effects of oxygen on formation of PCB and PCDD/F on extracted fly ash in the presence of carbon and cupric salt

The effect of oxygen-nitrogen atmosphere (N2 + 10%O2, N2 + 1%O2 and 99.999% N2) on the formation of PCB, PCDD and PCDF by the de novo synthetic reactions in the system consisting of extracted fly ash (from municipal waste incinerators--MWI), activated carbon, CuCl2 x 2H2O and NaCl at 340 degrees C was studied. The content of PCDD/F for systems with 10%O2, 1%O2 and 99.999% N2 was decreasing and corresponded to 17,304, 5544, and 1437 ng/sample. In all studied systems the isomer OCDD/F was prevailing. The content of PCBs in the same system was also decreasing from 1214 to 166 ng/g. Formation of nonortho PCB was relatively high compared to the system where only nitrogen was present. The possible mechanism of formation is outlined.