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1.
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.  相似文献   

2.
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.  相似文献   

3.
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.  相似文献   

4.
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.  相似文献   

5.
The formation and emission of dioxins in large scale thermal processes   总被引:15,自引:0,他引:15  
Everaert K  Baeyens J 《Chemosphere》2002,46(3):439-448
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.  相似文献   

6.
Xhrouet C  De Pauw E 《Chemosphere》2005,59(10):1399-1406
The sintering process is among the major sources of the very toxic polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in the environment. At the industrial scale, it has been shown that dust collected on the grid, which supports the feed, contains PCDD/Fs amounts between the values found in the bottom of the cake and the values found on dust collected during gas sampling in the wind boxes. This fact suggests that the grid, containing 25wt.% of chromium, could have a catalytic activity in PCDD/Fs formation during the sintering process. This research tries to study this potential role. The de novo synthesis of PCDD/Fs is simulated at laboratory scale by thermal treatments of samples mixed with grid filings or Cr2O3. The thermal experiments performed with E.S.P. dust (dust collected in the electrostatic precipitator of a sintering plant) or graphite mixed with grid filings do not allow to confirm a role of the grid in PCDD/Fs formation during the industrial process. On the other hand, it has been shown that Cr2O3 can be considered as a catalyst in the de novo synthesis of PCDD/Fs. This compound takes place in the two steps of the de novo synthesis: the degradation of the carbon matrix as well as the chlorination reactions.  相似文献   

7.
Bottom ash that was the result of the combustion of chromated copper arsenate (CCA) treated wood under controlled fire conditions showed an increase of several orders of magnitude in the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), compared to that of untreated timber. Wood that has been pressure treated with CCA contains copper (II), which is known to catalyse the so-called de novo formation of PCDD/Fs. Comparable levels of PCDD/Fs would be expected in residual ash from burning CCA-treated wood in backyard fires, stoves and wood heaters, as a consequence of similar combustion conditions.  相似文献   

8.
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.  相似文献   

9.
A survey to estimate the polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) emissions of Spanish hot dip galvanising sector was carried out during 2002. This investigation is the first presenting Spanish experimental data related to this industrial sector. Three different matrices: flue gas, ash and filter dust were tested to quantify the PCDD/Fs generated during the galvanising process. The organic source of PCDD/F formation could be from the insufficient degreasing o from inhibitors or additives used in the pickling steps such as quinoline, isoquinoline, 8-methylquinoline or polyether phosphoric acid. Low levels PCDD/Fs were achieved in air emissions when air control devices are used. On the contrary, filter dusts are highly contaminated; indicating that the absence of air control devices would increase the risk of fugitive emissions. Homologue profiles and Principal Component Analysis demonstrate there are differences in the formation mechanisms in the bath zone (ashes) compared to the stack location (filter dusts and air emissions), related to the de novo synthesis and reaction time. The annual PCDD/F emission to the atmosphere for this sector during 2002 has been estimated in 0.023g I-TEQ. The emission factor of plants with air control devices has been calculated at 0.030microg I-TEQ/ton of galvanised steel.  相似文献   

10.
Over the past decades in China, the number of medical waste incinerators (MWIs) has been rising rapidly, causing emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). In this study, samples of fly ash, ash deposits, and bottom ash from typical MWIs were analyzed for PCDD/Fs and their distribution characteristics. Results showed international toxic equivalent (I-TEQ) values in the range of 6.9–67 ng I-TEQ/g in fly ash and ash deposits, whereas the concentration in bottom ash was extremely low (only 1.33 pg I-TEQ/g), yet the generation of PCDD/Fs was mostly de novo synthesis in fly ash and ash deposits according to the ratio of PCDFs to PCDDs; the major distribution differences of PCDD/Fs in fly ash was manifested by the content of toxic furan 2,3,7,8-TCDF, but other toxic PCDD/Fs showed similar distribution. Other findings are that 2,3,4,7,8-PeCDF had the most contribution to TEQ concentration, and that the most abundant toxic furan congener is 1,2,3,4,6,7,8-HpCDF. Correlation analysis showed that there was no significant correlation between PCDD/Fs concentration and several other physical and chemical parameters.

Implications: This paper is of interest because it presents the emission performances of PCDD/Fs in ash from medical waste incineration in China. PCDD/F contents in fly ash and ash deposits vary between 6.9 and 67.3 ng I-TEQ/g. However, the concentration in bottom ash was extremely low (only 1.33?×?10?3 ng I-TEQ/g). The fingerprints of PCDD/Fs in fly ash are almost similar, except for 2,3,7,8-TCDF. There is no marked correlation between PCDD/Fs and other physicochemical properties.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.  相似文献   

11.
Formation and mitigation of PCDD/Fs in iron ore sintering   总被引:1,自引:0,他引:1  
Ooi TC  Lu L 《Chemosphere》2011,85(3):291-299
The sintering of iron ore is presently a significant industrial source of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) worldwide owing to the fundamental requirement of the operation of a high temperature process to pre-treat fines and to recycle plant by-products arising from the integrated iron and steelworks. The process is a noteworthy contributor of PCDD/F indirectly due to decreasing PCDD/F releases from municipal solid waste incineration. Commonly PCDD/F formation from the process is associated with the addition of oily mill scales although raw material containing a combination of C, Cl and specific metal catalyst has been shown to drastically increase PCDD/F formation in the process. The degenerate graphitic structure of carbon present in coke fuel and soot formed and the chemistry of catalytic metals and Cl are important factors. A review on PCDD/F emission in this process has been carried out, including examination of its formation mechanism, congener distribution, contributing factors and mitigation strategies, with emphasis on the use of inhibiting compound to achieve suppression. A detailed analysis of the de novo and precursor theories of formation and the contributing factor is given since the subject of PCDD/F formation is still controversial. The de novo formation pathway identified in sinter plants and controlled studies performed in the laboratory as well as at pilot-scale are discussed; where appropriate, a comparison is drawn between sintering and other thermal processes emitting PCDD/Fs. Summary of the latest developments in PCDD/F downstream abatement strategies presently employed in full scale industrial plants is provided. Potential inhibiting compounds are discussed in terms of their mode of action and merits under sintering conditions.  相似文献   

12.
Huang H  Buekens A 《Chemosphere》2001,44(6):1505-1510
A kinetic model is developed for de novo synthesis of PCDD/F from carbon in incinerator fly ash. The main mechanistic steps considered in the model are carbon gasification, PCDD/F formation, desorption and degradation. Rate equations are derived which can relate PCDD/F formation with process variables including carbon concentration of fly ash, partial pressure of oxygen, reaction temperature and time. The kinetic model has been verified using laboratory de novo synthesis data reported in the literature. When the model is applied to industrial incinerator conditions, PCDD/F formation levels of 0.1-0.5 microg/N m3 in the gas phase and 0.1-1.2 microg/g in the solid phase are calculated, and both are in good agreement with incinerator measurements.  相似文献   

13.
Unintentionally produced persistent organic pollutants (UP-POPs) including polychlorinated dibenzo-p-dioxins, and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs) were characterized and quantified in stack gas and fly ash from the second ventilation systems in five typical converters in five different steelmaking plants. The 2378-substituted PCDD/Fs (2378-PCDD/Fs) and dioxin-like PCB (dl-PCBs) toxic equivalents (TEQs) were 1.84–10.3 pg WHO-TEQ Nm?3 in the stack gas and 5.59–87.6 pg WHO-TEQ g?1 in the fly ash, and the PCN TEQs were 0.06–0.56 pg TEQ Nm?3 in the stack gas and 0.03–0.08 pg TEQ g?1 in the fly ash. The concentrations of UP-POPs in the present study were generally lower than those in other metallurgical processes, such as electric arc furnaces, iron ore sintering, and secondary metallurgical processes. Adding scrap metal might increase UP-POP emissions, indicating that raw material composition was a key influence on emissions. HxCDF, HpCDF, OCDF, HpCDD, and OCDD were the dominant PCDD/Fs in the stack gas and fly ash. TeCB and PeCB were dominant in the stack gas, but HxCB provided more to the total PCB concentrations in the fly ash. The lower chlorinated PCNs were dominant in all of the samples. The 2378-PCDD/F, dl-PCB, and PCN emission factors in stack gases from the steelmaking converter processes (per ton of steel produced) were 1.88–2.89, 0.14–0.76, and 229–759 μg t?1, respectively.  相似文献   

14.
Particle-bound polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) were monitored at two sites in northern Greece for an eight-month period in 1999. PCDD/F concentrations were close to the lower end of reported values worldwide. Excepting a few cases, the PCDD/Fs homologue profile was stable. The gaseous PCDD/F fractions calculated were found to account for a small percentage of the total concentrations (<2% for OCDD/Fs and HpCDD/Fs, while 30-35% for TCDFs). Particle-bound PCBs were also found at low concentrations which, however, were higher at the urban site. Calculations of the dry deposition of particulate PCDD/ Fs and PCBs gave mean values of 0.52 and 0.59 pg I-TEQ/m2/day of PCDD/Fs, while 242 and 74 pg/m2/day of sigmaPCBs for the urban and the semirural areas respectively. An anticorrelation of PCDD/F concentrations with ambient temperature was derived particularly for the lower chlorinated congeners. A weak association with winds of western and southern origin was also observed. Factor analysis and literature source profiles were employed to identify possible emission sources. It was appeared that the PCDD/F compositional pattern of TSP is influenced by mixed sources the most prominent being uncontrolled fires and car exhausts.  相似文献   

15.
Kim BH  Lee SJ  Mun SJ  Chang YS 《Chemosphere》2005,58(11):1589-1599
Many studies have been conducted that monitor and trace the sources of polychlorinated dibenzo-p-dioxin/furans (PCDD/Fs) by comparing congener patterns of environmental samples with those of possible sources. In this study, we measured PCDD/F concentrations and compared congener patterns of samples of various media found in and around an industrial waste incinerator in Korea, including stack gas, fly ash, bottom ash, ambient air, soil, pine needle, and human blood. We obtained reliable data on the relationship between the PCDD/F distributions in these sources and the environment, and thus found indicators with which to assess the impact of such sources on the surrounding environment. In addition, the difference between the levels of PCDD/Fs in the blood of short-term workers and long-term workers demonstrates that these workers are exposed to the compounds produced by the indicator.  相似文献   

16.
Jin GZ  Lee SJ  Kang JH  Chang YS  Chang YY 《Chemosphere》2008,70(9):1568-1576
Polyethylene (PE) and polyvinyl chloride (PVC) are the leading plastics in total production in the world. The incineration of plastic-based materials forms many chlorinated compounds, such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). In this study the addition of goethite (alpha-FeOOH) was investigated to determine its suppressing effect on the emission of PCDD/Fs and hexachlorobenzene (HCB) during the combustion of wastes containing PE and PVC. Goethite was being considered since it acts as a dioxin-suppressing catalyst during incineration. Results showed that incorporation of goethite greatly reduced the generation of PCDD/Fs and HCB in the exhaust gas and fly ash. The concentration of PCDD/Fs in flue gas decreased by 45% for lab-scale and 52% for small incinerator combustion experiments, where the goethite ratios in feed samples were 0.54% and 0.34%, respectively. Under the same conditions, the concentration of HCB in flue gas decreased by 88% and 62%, respectively. The present study showed a possible mechanism of the suppressing effect of the goethite for PCDD/F formation. It is likely that iron chlorides react with particulate carbon to form organo-chlorine compounds and promote PCDD/F formation in the gas phase. XRD analysis of combustion ash revealed that the goethite was partially dehydrated and converted to alpha-Fe(2)O(3) and Fe(3)O(4) but no iron chlorides formation. Therefore the goethite impregnated plastics can contribute the reduction of PCDD/Fs and HCB in the exhaust gas during incineration of MSW.  相似文献   

17.
This study shows the catalyzing effects of iron and copper on the formation of chlorinated compounds such as chlorobenzenes (ClBzs), chlorophenols (CIPhs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Both total concentrations and congener distributions have been studied. The parameters and conditions varied during the combustion tests were the complete and incomplete combustion and the metal and chlorine addition. The incomplete combustion promoted the formation of organic chlorinated compounds in flue gas particles. Highly chlorinated congeners of PCDD/F were dominant in the flue gas particles, whereas the importance of lower chlorinated congener were increased in the gas phase. In the complete combustion conditions the concentrations of PCDD/Fs increased when the degree of chlorination were high, nevertheless the concentrations of tetra and penta PCDD/Fs were higher in the gas phase than the concentrations in the fly ash particles. Organic chlorine promoted the formation of chlorinated compounds more effectively than inorganic chlorine, which instead promoted the formation of PCDD/Fs in the gas phase, especially with copper catalyst. Different concentration levels of chlorinated compounds were observed in the gas phase and in particles when the chlorine source and combustion conditions were varied from incomplete to optimum conditions. Both copper and iron seem to have a catalytic effect on PCDD/F formation.  相似文献   

18.
Catalytic oxidation of gaseous PCDD/Fs with ozone over iron oxide catalysts   总被引:2,自引:0,他引:2  
Wang HC  Chang SH  Hung PC  Hwang JF  Chang MB 《Chemosphere》2008,71(2):388-397
Catalytic oxidation of PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) with ozone (catalytic ozonation) over nano-sized iron oxides (denoted as FexOy) was carried out at temperature of 120-180 degrees C. The effects of operating temperature, ozone concentration, space velocity (SV) and water vapor contents on PCDD/F removal and destruction efficiencies via catalytic ozonation were investigated. High activity of the iron oxide catalyst towards PCDD/F decomposition was observed even at low temperatures with the aid of ozone. The PCDD/F removal and destruction efficiencies achieved with FexOy/O3 at 180 degrees C reach 94% and 91%, respectively. In the absence of ozone, the destruction efficiencies of all PCDD/F congeners are below 20% and decrease with increasing chlorination level of PCDD/F congener at lower temperature (120 degrees C). However, in the presence of ozone, the destruction efficiencies of all PCDD/F congeners are over 80% on FexOy/O3 at 180 degrees C. Higher temperature and ozone addition increase the activity of iron oxide for the decomposition of PCDD/Fs. Additionally, in the presence of 5% water vapor, the destruction efficiency of the PCDD/Fs is above 90% even at lower operating temperature (150 degrees C). It indicates that the presence of appropriate amount of water vapor enhances the catalytic activity for the decomposition of gas-phase PCDD/Fs.  相似文献   

19.
Duo W  Leclerc D 《Chemosphere》2007,67(9):S164-S176
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.  相似文献   

20.
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.  相似文献   

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