The effects of temperature and oxygen content on the PCDD/PCDFs formation in MSW fly ash

In this study, the effects of the temperature, oxygen content in the gas stream and carbon content in ash particles on PCDD/Fs formation on the fly ash surface were investigated. The optimum temperatures for dioxin formation were found at 350 degrees C for boiler ash, 300 degrees C for cyclone ash and 250 degrees C for ESP ash, respectively. Preliminary results indicate that the optimum temperature will decrease as the particle size decreases. When the O2 concentration is varied between 0% and 100%, the optimum oxygen content for PCDD/Fs formation is found to be at 7.5% for cyclone ash, and the PCDD/PCDF ratio increases with the increase of oxygen content. Dioxin formation is observed even for the gas containing no oxygen passed through the fly ash. Hence, other reacted routes that do not need O2 for dioxin formation take place on fly ash. The carbon content in fly ash is varied between 0% and 20% in this study, and the results have indicated that the maximum dioxin formation is to be found at 5%. The precursors are not injected into the fly ash or gas stream in all formation experiments, however, dioxin is still formed in fly ash. Consequently, other chlorinated routes besides Deacon reactions may take place on the fly ash surface.     

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).     

The toxicity and toxic potential of fly ash from municipal incinerators assessed by means of a fish early life stage test

The toxicity and toxic potential of fly ash were assessed, using rainbow trout yolk sac fry. In contrast to fly ash itself, extracts of fly ash were extremely toxic, producing typical toxicopathological features of TCDD-intoxication. By comparison with earlier experiments using pure 2,3,7,8-TCDD, the toxic potential of fly ash was roughly estimated to be 75–125 ng.g^?1 toxic aequivalents TCDD. Obviously, this toxic potential is attributable for a minor part to 2,3,7,8-TCDD and for the greater part to the other chlorinated dioxin congeners and the dibenzofurans, present in fly ash.     

Systematic analysis and overall toxicity evaluation of dioxins and hexachlorobenzene in human milk

A systematic method for analyzing dioxins (PCDDs, PCDFs and dioxin-like PCBs), hexachlorobenzene (HCB), heptachlor epoxide and beta-hexachlorocyclohexane (HCH) in human milk was developed to determine the residual amount of HCB in human milk and to evaluate the overall toxicity of both dioxins and HCB in human milk. The fractionation behavior of HCB on chromatography with silica gel, alumina, and activated carbon/silica gel, and the concentrated sulfuric acid decomposition method, which is widely used as a dioxin cleanup method, were studied in order to make the preprocessing operation for HCB measurement compatible with that for conventional dioxin measurement. HCB was found to be eluted in the 2% dichloromethane (DCM)/hexane 60 ml fraction from an alumina column. Heptachlor epoxide and a part of beta-HCH were eluted in the 10% DCM/hexane 50 ml fraction from a silica gel column, while the remaining beta-HCH was eluted in the 25% DCM/hexane 60 ml fraction from an activated carbon/silica gel column. Moreover, HCB showed significant correlation with dioxin congeners having high toxicity equivalence factors (TEFs). The results suggest that the exposure route to HCB and its accumulation behavior in the human body are similar to those of the dioxins.     

Dehalogenation potential of municipal waste incineration fly ash

BACKGROUND, AIMS AND SCOPE: It is well known that the fly ash from filters of municipal waste incinerators (MWI-FA) shows dehalogenation properties after heating it to 240-450 degrees C. However, this property is not general, and fly ash samples do not possess dehalogenation ability at all in many cases. Fly ash has a very variable composition, and the state of the fly ash matter therefore plays the decisive role. In the present paper, the function of important components responsible for the dehalogenation activity of MWI-FA is analysed and compared with the model fly ash. METHODS: With the aim of accounting for the dehalogenation activity of MWI-FA, the following studies of hexachlorobenzene (HCB) dechlorination were performed: The role of copper in dehalogenation experiments was evaluated for five types of metallic copper. The gasification of carbon in MWI-FA was studied in the 250-350 degrees C temperature range. Five different kinds of carbon were used, combined with conventional Cu(o) and activated nanosize copper powder. The dechlorination experiments were also carried out with Cu(II) compounds such as CuO, Cu(OH)2, CuCl2 and CuSO4. The results were discussed from the standpoint of thermodynamics of potential reactions. Based on these results, the model of fly ash was proposed, containing silica gel, metallic copper and carbon. The dechlorination ability of MWI-FA and the model fly ash are compared under oxygen-deficient atmosphere. CONCLUSIONS: The results show that, under given experimental conditions, copper acts in the dechlorination as a stoichiometric agent rather than as a catalyst. The increased surface activity of copper enhances its dechlorination activity. It was found further that the presence of copper leads to a decrease in the temperature of carbon gasification. The cyclic valence change from Cu(o) to Cu+ or Cu2+ is a prerequisite for the dehalogenation to take place. RECOMMENDATION AND OUTLOOK: Thermodynamic analysis of the dechlorination effect, as well as the comparison of dechlorination pathways on MWI-FA and model fly ash, can provide a deeper understanding of the studied reaction.     

Adsorption and chlorination of dibenzo-p-dioxin and 1-chlorodibenzo-p-dioxin on fly ash from municipal incinerators

Adsorption and chlorination reactions for dibenzo-p-dioxin (DD) and 1-chlorodibenzo-p-dioxin (1-MCDD) on fly ash were characterized quantitatively using laboratory-based simulation of stack emissions with air and HCl-air atmospheres. Influences of contact time and temperature were studied and results showed behavior of DD and 1-MCDD consistent with that for 1,2,3,4-tetrachlorodibenzo-p-dioxin. Di-, tri-, and tetra-chlorinated dioxins were major compounds produced from heterogenous phase reactions of DD and 1-MCDD with HCl in air. Total conversion through reactions alone were as high as 81% and 58% respectively.     

Formation of dioxins (PCDDs/PCDFs) by dioxin-free fly ash as a catalyst and relation with several chlorine-sources

Simplified thermal formation experiments have been conducted using dioxin-free fly ash as a catalyst with many kinds of combustible samples such as newspaper, kerosene, paraffin, PE (polyethylene), PP (polypropylene) and PVC. Chlorine sources were PVC, NaCl and HCl. The combustion of samples containing chlorine in the absence of dioxin-free fly ash produced dioxins at a low level although HCl was present in the gas stream. On the other hand, the combustion of samples without chlorine with dioxin-free fly ash increased dioxins formation to a level around 10 times higher than that upon heating dioxin-free fly ash alone. This result is considered to be due to the presence of metal chloride in the fly ash and hydrocarbons in the gas stream. The combustion of samples containing either an organic or inorganic chlorine source or using a HCl stream with dioxin-free fly ash increased dioxin level dramatically.     

Chlorination reactions of 1,2,3,4-tetrachlorodibenzo-p-dioxin on fly ash with HC1 in air

Chlorine substitution reactions of 1,2,3,4-TCDD to higher chlorinated PCDD occurred on fly ash between 50°C to 250°C with an HC1 in air atmosphere in a laboratory reaction apparatus used to simulate emission conditions in municipal incinerators. Percent conversion of 1,2,3,4-TCDD through such reactions was as high as 66% by mass corrected for losses to irreversable absorption. Production of penta-, hexa-, hepta- and octa-CDD was evident and a maximum in production of P₅CDD and H₆CDD was reached in 10 to 30 min. Results showed that these reactions may involve complex mechanisms which include several states of adsorption with different reactivities of 1,2,3,4-TCDD on fly ash.     

Dioxin contents in fly ash from large-scale MSW incinerators in Taiwan

In this study, fly ash samples were collected from three municipal waste incinerators (MWI) in Taiwan. These MWIs investigated are equipped with different air pollution control devices (APCDs). Preliminary results indicated that 2,3,7,8-PCDD/Fs homologue patterns of various types of fly ash were quite similar for all three MWIs. Concentrations of higher-chlorinated congeners of PCDDs and PCDFs were remarkably higher than those of lower-chlorinated congeners. In the case of MSW-A, the PCDD/PCDF ratios of ashes were found in the decreasing order for cyclone, boiler and baghouse. The PCDD/PCDF ratios in various types of fly ash of MWI-B was boiler-A < boiler-B < ESP < boiler-C. As for MSW-C, no obvious trend has been observed for PCDD/PCDF ratio. However, the ratio in boiler ash was higher than that in baghouse ash of MWI-A. The dioxin contents in fly ash would increase as the fly ash passed through APCD zones. In other words, the environmental conditions of APCD may actually cause the increase of the dioxin contents in fly ash. The trend for dioxin contents in fly ash collected from three MSW incinerators investigated was MSW-C < MSW-A < MSW-B.     

Dechlorination/hydrogenation and destruction reactions of PCDDs in OCDD-added fly ash heated under vacuum

Octachlorodibenzo-p-dioxin (OCDD)-added, pretreated fly ash was heated under vacuum at sample temperatures ranging from T(s)=450 to 650 K. The fly ash and liquid nitrogen-cooled trap samples were analyzed for DD/DF through OCDD/DF. The total amounts of DD through OCDD decrease with increasing T(s), which indicates that dechlorination/hydrogenation (DCH) reactions are not the only reaction channels. Reduction of toxic equivalent (TEQ) for PCDDs by more than 99% was achieved in the fly ash by the vacuum heat treatment at T(s)=650 K for 4 h. The total amount of PCDDs and DD detected in the liquid nitrogen-cooled trap relative to that of added OCDD was about 17%, i.e., PCDDs and DD which were adsorbed to the fly ash surfaces can evaporate into the gaseous phase. The difference between the evaporation behavior of PCDDs in the present and the previous studies is discussed in the light of their states of existence.     

Surface catalyzed halogenation-dehalogenation reactions of aromatic bromine compounds adsorbed on fly ash

Brominated aromatic compounds like brominated benzenes, diphenylethers and dibenzodioxins adsorbed on the surface of fly ash from a municipal waste incininerator give mixed brominated/chlorinated und completely chlorinated aromatic compounds. These consecutive halogenation-dehalogenation reactions proceed by a nucleophilic mechanism, which is favoured by a high concentration of chloride on the fly ash. Results of kinetic and stereoselective behavior of these reactions will be discussed. The relevance of these results for PCDD/PCDF formation from bromine precursors in municipal waste incinerators will be discussed.     

Removal of PCDDs/DFs and dl-PCBs in MWI fly ash by heating under vacuum

Temperature dependence of PCDD/DF and dioxin-like polychlorinated biphenyl (dl-PCB) concentrations in fly ash from a municipal waste incinerator (MWI) heated under vacuum has been investigated as a function of sample temperature ranging from T(s)=425 to 800 K to find out if PCDDs/DFs in fly ash evaporate and are trapped in a liquid nitrogen-cooled trap. The results show that more than 99.98% of PCDDs/DFs in TEQ is removed from fly ash by vacuum heat treatment at T(s)>650 K for 4 h. Almost no PCDDs/DFs were detected in the liquid nitrogen-cooled trap. Homologue distributions indicate that dechlorination/hydrogenation (DCH) reactions proceed in fly ash at T(s)>450 K. Arrhenius rate parameters for the DCH reactions have been determined for each homologue assuming that only DCH reactions occur. The fly ash heated under vacuum at 650 or 800 K was reheated at 573 K (300 degrees C) in a stream of dry or humid air to see how much PCDDs/DFs and dl-PCBs are regenerated. We have found that (1) PCDDs/DFs are regenerated in both 650 K and 800 K treated fly ash, whereas dl-PCBs are regenerated in 650 K treated fly ash, (2) formation of PCDFs predominates over that of PCDDs or dl-PCBs, and (3) less chlorinated homologues are abundant for PCDDs/DFs and dl-PCBs.     

Thermal removal of PCDD/Fs from medical waste incineration fly ash--effect of temperature and nitrogen flow rate

The fly ash used in this study was collected from a bag filter in a medical waste rotary kiln incineration system, using lime and activated carbon injection followed by their collection as mixed fly ash. Experiments were conducted on fly ash in a quartz tube, heated in a laboratory-scale horizontal tube furnace, in order to study the effect of temperature and nitrogen flow rate on the removal of PCDD/Fs. Results indicated that in this study PCDD/Fs in the fly ash mostly were removed and desorbed very little into the flue gas under thermal treatment especially when the heating temperature was higher than 350 °C, and dechlorination and destruction reactions took important part in the removal of PCDD/Fs. However, in terms of flow rate, when flow rate was higher than 4 cm s⁻¹, destruction efficiency of PCDD/Fs decreased dramatically and the main contributors were P₅CDF, H₆CDF and H₇CDF desorbed to flue gas, the PCDD/Fs in the fly ash decreased with enhanced flow rate.     

The effect of copper speciation on the formation of chlorinated aromatics on real municipal solid waste incinerator fly ash

A limited amount of information exists regarding the relationship between the chemical form of copper and the formation of chlorinated aromatics in fly ash. To understand the effects of the various forms of copper on the formation of chlorinated aromatics in real fly ash, we determined the chemical forms of copper present in various types of real fly ash using X-ray absorption near edge structure (XANES) and evaluated the relationship between the chemical forms of copper and the formation of chlorinated aromatics. Copper chloride hydroxide (CuCl2 x 3Cu(OH)2) and cuprous chloride (CuCl) were the predominant copper species found in real fly ash. Although pure cupric chloride (CuCl2) is known to be the most active catalyst for the formation of chlorinated aromatics under experimental conditions with synthetic fly ash, CuCl2 was not found in every real fly ash sample. The amount of copper chloride hydroxide was positively correlated with the formation of chlorinated aromatics in real fly ash and is, consequently, considered to be one of the key species involved in the formation of chlorinated aromatics.     

Optimization of the purification method for dioxin analysis in human serum and temporal changes in background dioxin levels in the general population

To perform high quality and high throughput measurements, complicated purification procedure by two rounds of open column chromatography was simplified by appraising the components and adding a sufficient amount of adsorbents to the column. The procedure consists of two open column techniques using a multi-layer silica gel column and an active carbon dispersed silica gel column. This purification procedure is used in "Standard manual for dioxin analysis in human blood" published in 2000 (Ministry of Health and Welfare, Japan, 2000). Consequently, a purification procedure using only 1 g of 10% AgNO(3)/silica gel can remove the matrix of blood serum as effectively as a multi-layer silica gel column. In addition, 0.1 g of carbon silica gel, equivalent to 1/10 the weight used currently in analyses, separates and recovers the dioxins in purified extract of blood serum. Furthermore, changes in the background level in the general population were clarified by monitoring the dioxin concentrations in human blood. The dioxin concentrations and ratios in blood in the general population remained at a tolerable level for three months. Therefore, the blood serum was available for the detection of a remarkable elevation in dioxins level considered to be indicative of contamination due to high-density exposure.     

Predicting extents of mercury oxidation in coal-derived flue gases

The proposed mercury (Hg) oxidation mechanism consists of a 168-step gas phase mechanism that accounts for interaction among all important flue gas species and a heterogeneous oxidation mechanism on unburned carbon (UBC) particles, similar to established chemistry for dioxin production under comparable conditions. The mechanism was incorporated into a gas cleaning system simulator to predict the proportions of elemental and oxidized Hg species in the flue gases, given relevant coal properties (C/H/O/N/S/Cl/Hg), flue gas composition (O2, H2O, HCl), emissions (NO(X), SO(X), CO), the recovery of fly ash, fly ash loss-on-ignition (LOI), and a thermal history. Predictions are validated without parameter adjustments against datasets from lab-scale and from pilot-scale coal furnaces at 1 and 29 MWt. Collectively, the evaluations cover 16 coals representing ranks from sub-bituminous through high-volatile bituminous, including cases with Cl2 and CaCl2 injection. The predictions are, therefore, validated over virtually the entire domain of Cl-species concentrations and UBC levels of commercial interest. Additional predictions identify the most important operating conditions in the furnace and gas cleaning system, including stoichiometric ratio, NO(X), LOI, and residence time, as well as the most important coal properties, including coal-Cl.     

Assessment of PCDD/F and PBDD/F emissions from coal-fired power plants during injection of brominated activated carbon for mercury control

The effect of the injection of brominated powdered activated carbon (Br-PAC) on the emission of brominated and chlorinated dioxins and furans in coal combustion flue gas has been evaluated. The sampling campaigns were performed at two U.S. Department of Energy (DOE) demonstration sites where brominated PAC was being injected for control of mercury emissions. The results of the sampling campaigns showed that injection of the brominated PAC upstream of the electrostatic precipitator (ESP) did not increase the emissions of total and Toxic EQuivalent (TEQ) chlorinated and brominated dioxin compounds. Rather, the data suggested the sorbent may capture these compounds and reduce their concentration in the flue gas stream. This effect, when seen, was small, and independent of the type of plant emission controls, temperature at the point of injection, or fuel-chlorine content. The addition of the brominated PAC sorbent resulted in slight increases the total content of chlorinated dioxins and furan in the particulate matter (ash) collected in the ESP, but did not increase its overall toxicity.     

Strength Development of Solidified/Stabilized Organic Waste and Optimum Treatment Design

Abstract

Artificially contaminated (spiked) natural soils were solidified/stabilized using various combinations of commonly used additives, such as lime, cement, fly ash, activated carbon, and silica fume. The effectiveness of the solidification/stabilization (S/S) processes was evaluated based on experimental findings from compaction testing, unconfined compressive shear strength, and X-ray diffraction (XRD). Correlations of limited reliability between unconfined compressive strength and penetrometer and torvane measurements were derived. Results from XRD experiments indicated that certain organic contaminants (i.e., naphthalene and pyrene) might impact the S/S processes for a given combination of additives. The type and amount of organic contaminants also affected the pozzolanic reactions. Specifically, the absence or small peak intensity of pozzolanic product XRD patterns for a given combination of additives was a good indication that the type and the amount of organic contaminant present inhibited pozzolanic reactions. This phenomenon was tested and confirmed for actual field-contaminated samples.     

A pilot study of mercury liberation and capture from coal-fired power plant fly ash

The coal-fired electric utility generation industry has been identified as the largest anthropogenic source of mercury (Hg) emissions in the United States. One of the promising techniques for Hg removal from flue gas is activated carbon injection (ACI). The aim of this project was to liberate Hg bound to fly ash and activated carbon after ACI and provide high-quality coal combustion products for use in construction materials. Both bench- and pilot-scale tests were conducted to liberate Hg using a thermal desorption process. The results indicated that up to 90% of the Hg could be liberated from the fly ash or fly-ash-and-activated-carbon mixture using a pilot-scale apparatus (air slide) at 538 degrees C with a very short retention time (less than 1 min). Scanning electron microscope (SEM) evaluation indicated no significant change in fly ash carbon particle morphology following the thermal treatment. Fly ash particles collected in the baghouse of the pilot-scale apparatus were smaller in size than those collected at the exit of the air slide. A similar trend was observed in carbon particles separated from the fly ash using froth flotation. The results of this study suggest a means for power plants to reduce the level of Hg in coal-combustion products and potentially recycle activated carbon while maintaining the resale value of fly ash. This technology is in the process of being patented.     

Destruction of dioxins and furans adsorbed on flyash in a rotary kiln furnace

The paper deals with the use of a rotary kiln furnace for thermal destruction of dioxin combined with a baghouse filter for the recycling of entrained flyash and an activated carbon filter for adsorbtion of dioxin traces transported by gas phase.Measurements performed at a pilot plant with a throughput of 200 kg flyash/hr revealed 99.5 % destruction of dioxins and furans. Furthermore, the destruction of all organics, 95 % desorbtion of mercury and quantitative elimination of peripheral (located at the surface) Chromium (CrVI) were achieved.An activated carbon filter placed in the fluegas stream of an municipal waste incinerator was started up to investigate the influence of interfering constituants like SO₂, HCl etc. on the filter performance. Loading data, removal efficiency and make up performance were collected.