焚烧炉中二恶英废气的产生与控制方法探讨

文中详述了焚烧炉中二恶英废气产生的原因,针对产生原因提出控制方法,并总结出治理二恶英废气的措施。提出了今后对二恶英的控制建议。     

Abundance and sources of ambient dioxins in Hong Kong: a review of dioxin measurements from 1997 to 2001

Ambient measurements of seventeen 2,3,7,8-polychlorinated dibenzo-p-dioxin/dibenzofuran congeners (2,3,7,8-PCDD/Fs) have been taken in a number of monitoring programs or ad-hoc studies in Hong Kong. The longest monitoring program started at two locations in the territory in July 1997. The other monitoring efforts are ad-hoc studies, varying from a few coordinated sampling events at multiple sites to a year-long monitoring project that targeted suspected local dioxin sources. In this paper, we examined these measurements to understand the ambient levels, temporal and spatial variation, and possible sources of the 2,3,7,8-PCDD/Fs in Hong Kong. The territory-wide annual average concentration of the dioxins was 0.052 pg I-TEQ/m3 measured at the regular monitoring stations in the most recent annual cycle of 2000/2001. This level fell at the lower end of the range of dioxin concentrations measured at other urban locations around the world. The dioxin levels showed a clear seasonality in that elevated concentrations were observed in the winter and lower concentrations in the summer at all monitoring sites with one year or more regular measurements. The measurements indicated that the few known local dioxin sources, including a major chemical waste incinerator facility, landfill sites, and vehicular traffic, are not important contributors to ambient dioxins in Hong Kong. On days of high dioxin concentrations, the 2,3,7,8-PCDD/F congeners were observed to have almost identical compositions with a north-northwest to south-southeast spatial gradient in concentrations at different sampling locations in Hong Kong. This observation, along with other collaborative evidence, established a strong link between high dioxin concentration days in Hong Kong and regional transport of the polluted air masses from the north.     

垃圾焚烧发电过程中的二次污染物控制处理技术

概述了二口恶英、重金属、酸性气体、灰渣等垃圾焚烧二次污染物的形成机理，并详细介绍了通过控制垃圾焚烧条件、尾气处理以及吸附等方法，可以有效控制二口恶英类污染物的排放；重金属的控制可以用除尘器或使用相应的吸附剂处理；采用较为成熟的烟气处理技术，可以控制处理酸性气体；灰渣可采用固化稳定化和酸或其他溶剂提出法处置。     

Gas-phase mechanism for dioxin formation

We consider the formation of dioxin in the gas phase through the combination of phenoxy radicals in the context of a recently published scenario regarding the possibility of forming highly chlorinated benzenes in poorly mixed systems. It is demonstrated that the production of free chlorine in fuel lean combustion systems and subsequent mixing and quenching with fuel rich mixtures leads to chlorine atoms as the main reactive radicals. Under such conditions high concentrations of chlorinated phenoxy radicals can be formed. This leads to the formation of concentrations of dioxins that are consistent with recent measurements of Sidhu et al. [Combust. Flame 100 (1995) 11]. It suggests that there may be a gas-phase channel for the dioxin formation in addition to the usually assumed surface catalyzed process.     

An assessment of dioxin contamination from the intermittent operation of a municipal waste incinerator in Japan and associated remediation

Significant dioxin (polychlorinated dibenzo-para-dioxins (PCDDs)/polychlorinated dibenzo-furans (PCDFs)) pollution from a municipal solid waste incinerator was discovered in 1997 in Osaka prefecture/Japan. The cause and mechanism of pollution was identified by a detailed assessment of the environment and incinerator plant. The primary sources of PCDD/PCDF pollution were high dioxin releases from an intermittently operated waste incinerator with PCDD/PCDF emissions of 150 ng-TEQ/Nm³. PCDD/PCDF also accumulated in the wet scrubber system (3,000 μg TEQ/L) by adsorption and water recirculation in the incinerator. Scrubber water was air-cooled with a cooling tower located on the roof of the incinerator. High concentrations of dioxins in the cooling water were released as aerosols into the surrounding and caused heavy soil pollution in the area near the plant. These emissions were considered as the major contamination pathway from the plant. Decontamination and soil remediation in and around the incinerator plant were conducted using a variety of destruction technologies (including incineration, photochemical degradation and GeoMelt technology). Although the soil remediation process was successfully finished in December 2006 about 3 % of the waste still remains. The case demonstrates that releases from incinerators which do not use best available technology or which are not operated according to best environmental practices can contaminate their operators and surrounding land. This significant pollution had a large impact on the Japanese government’s approach toward controlling dioxin pollution. Since this incident, a ministerial conference on dioxins has successfully strengthened control measures.     

Characteristics of dioxin emissions at startup and shutdown of MSW incinerators

Dioxin concentrations from municipal waste incinerators in Japan and elsewhere often show low concentrations that comply with legal limits (in this paper, the term "dioxin" designates WHO-TEQ: PCDD/Fs+dioxin-like PCB). However, such data is usually generated under normal steady state operational conditions, and there has been little investigation of releases occurring during startup and shutdown. It is important, therefore, to ascertain quantitatively emissions in an unsteady state (startup and shutdown) in order to correctly evaluate the relationship between emissions from a facility and the surrounding environment. The present study aimed to examine dioxin emissions of a continuously operated incinerator at startup and shutdown, and estimating the time period of greatest emission, and the processes causing dioxin generation. The startup process was divided into five stages and the shutdown into two; at each stage, dioxins in the flue gas were measured at the boiler outlet and the stack. From the concentration of dioxins and the flue gas volume at each stage, the amount of dioxins at startup and shutdown were calculated, and these were compared with that under steady state conditions. Dioxin concentration at the stack under steady state conditions was a very low level, while those at startup and shutdown were higher. In the case where dioxin concentration under a steady state is a low level like in this study, it is indicated that the total annual dioxin emission from a facility could be attributed to the startup periods.     

De novo formation characteristics of dioxins in the dry zone of an iron ore sintering bed

The objectives of this work are to understand the details of the mechanism of dioxin formation in the part of a sintering bed termed the dry zone, and to obtain ideas on how to prevent their formation. Sinter mixtures of various composition types were heated in a packed bed reactor, and dioxins in the outlet gas and in the sinter mixture residue were measured. The dioxin formation potential of a simple sinter mixture composed of iron ore, coke and limestone was markedly lower than that of fly ash from a municipal solid waste incinerator (MSWI). In consideration of this result, a series of experiments were conducted using a sinter mixture impregnated with CuCl2. Experimental results showed that dioxin formation was temperature-dependent in the range of 300-550 degrees C, with the maximum observed at around 300 degrees C, which was quite similar to that of fly ash from the MSWI. The homologue distribution of PCDD/Fs in gas and solid reflected the possible difference in carbonaceous materials in coke and activated coke. Gaseous hydrogen chloride acted as a chlorinating reagent for dioxin formation.     

Biomonitoring of PCDD/Fs in populations living near portuguese solid waste incinerators: levels in human milk

In the context of two Environmental Health Surveillance Programs, launched in response to public and scientific concern in relation to waste incinerators located near Lisbon and in Madeira Island, two human biomonitoring projects have been started in Portugal, focussed in dioxins and dioxin-like compounds in human milk. Results from the undertaken studies have already provided data on the extent and pattern of dioxin body burden of both studied groups as well as a preliminary temporal trend of dioxin levels for the population residing near Lisbon incinerator. The present paper investigates difference between exposed and non-exposed subjects under study and, from a preventive perspective, possible covariates of the dioxin levels in human milk. Emissions from both incinerators appear to be well controlled as there is no increase of human body burden of dioxins as measured in human milk of individuals living near these facilities. Concerning other determinants of dioxin levels, results suggest confirmation of previously found significant age-dependent trend towards higher levels of dioxins in aged subjects. On the contrary, association between mother's levels of dioxins and parity lost significance. Apart from the issue of incineration, the general conclusion for the general population is that living in Lisbon as compared to Madeira results in higher milk dioxin levels and possible health risks. The profile of the single congeners for PCDD/Fs in human milk from Madeira and Lisbon shows similar contributions for 12378-PCDD, 23478-PCDF, 123678-HCDD and 2378-TCDD, that account altogether for about 84% of the total identified dioxin body burden in the studied groups.     

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.     

Formation of toxic chemicals including dioxin-related compounds by combustion from a small home waste incinerator

We investigated combustion in a small home waste incinerator and analyzed both flue gas and residual ash for formation of the dioxin-related compounds polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and coplanar polychlorinated biphenyls and their precursors polychlorinated benzenes, polychlorinated phenols, polychlorinated diphenyl ethers, and polychlorinated biphenyls. Particularly, we investigated the effect of the incinerated material's composition on both the congener ratios of released compounds and the total concentration of all congeners of each compound. Eight different samples were prepared for incineration with four samples consist entirely paper, dead leaves, natural wood, or building materials. The remaining four samples contained mostly paper, but also other components such as fiber, non-chlorine-containing plastics, chlorine-containing plastics, and copper electric wire. The presence of non-chlorine-containing plastic in combustion samples did not increase overall dioxin or dioxin-precursor emissions. In contrast, chlorine-containing plastic resulted in a several-fold increase in total polychlorinated dioxins released, in both flue gas and residual ash. Copper wire resulted in a further several-fold increase in total polychlorinated dioxins and dioxin precursors released, with one exception: the addition of chlorine-containing plastic resulted in a many-fold increase in polychlorinated biphenyls, but only a modest further increase ( approximately 52%) with the further addition of copper. Homologue ratios tended toward higher-chlorine compounds as chlorine-containing plastic and Cu were added, but the results were far from uniform. Our results show that toxic dioxin release from small home waste incinerators must be considered significant, especially if even small amounts of chlorine-containing plastics or copper are burned.     

Dioxin-like potencies and extractable organohalogens (EOX) in medical, municipal and domestic waste incinerator ashes in Japan

Ash samples collected from medical, municipal and small-scale domestic incinerators in Japan were tested for dioxin-like activity using bioassay technique (ethoxyresorufin-O-deethylase: EROD assay) and for extractable organohalogens (EOX) using instrumental neutron activation analysis in order to estimate potential toxicity and responsible chemicals in those samples. Crude extracts and fractions cleaned-up for dioxin analysis from the samples were used for the analysis. The ranges of dioxins in the ashes were between 2.23 and 12.29 ng TEQ/g (dry weight). Relative potency ranges estimated by EROD assay in the medical incinerator ashes were 3.8-17.6 times higher than the results of conventional chemical analysis. EOX analysis suggested that ash samples contained plenty of organochlorine compounds apart from chlorinated dioxins. In addition, medical waste incinerator ashes were considered to have relatively higher amount of organoiodine compounds. In the cleaned-up fractions, bioassay potency ranges were lower than those in the crude extracts. However, some samples still exhibited higher potency than expected from chemical analysis. Though some polycyclic aromatic hydrocarbons were found in the fractions, the amounts were relatively low (0.39-10.56 ng/g). The results imply that some bioactive organohalogens that cannot be detected in the conventional chemical analysis might have potential for dioxin-like toxicity, and contribute to higher bioassay activities. The combination of the chemical analysis with the bioassay and EOX provides rough figure of dioxin-like toxicity and suggests types of organohalogen compounds that should be identified as a part of dioxin analysis for control emission from an incineration plant.     

Dispersion modelling of dioxin releases from the waste incinerator at Avonmouth,Bristol, UK

A modified Gaussian atmospheric dispersion model, Industrial Source Complex (ISCST3), is used to estimate toxic equivalent ground level concentrations (GLC) of dioxins emitted from the Avonmouth municipal waste incinerator (MWI) in Bristol, UK. The sensitivity of the predicted GLC to various vapour and particle partitioning scenarios is reported. Predictions incorporating local terrain and actual emission data are used to estimate the mean incremental intake of dioxin due to MWI operation for local residents, through an existing multi-pathway human exposure model. Results are compared with predictions of incremental intake for a generalised MWI. The mean incremental dioxin intake for a hypothetical maximum exposed individual (HMEI) is shown to be up to 46.5% of the background intake compared to only 1.14% for the generalised MWI scenario. This indicates that the use of local terrain and emission data in MWI dispersion modelling is crucial for health risk assessments associated with human dioxin intake, especially in view of the current debate over the tolerable daily intake for dioxins.     

Effects of dietary habits and CYP1A1 polymorphisms on blood dioxin concentrations in Japanese men

The major source of dioxin impurities in Japan in the past was agrochemical formulations; more recently, it has been exhaust from waste incinerators. To examine the environmental and genetic factors that influence blood dioxin concentration, we investigated the relationship among dioxin concentrations, dietary habits and cytochorome P450 1A1 (CYP1A1) polymorphisms (MspI type and Ile-Val type) in Japanese fishermen and farmers, including also a group of office workers as controls. The mean dioxin concentrations in the fishermen, the farmers and the controls were 161369, 79079 and 100500 pg/g fat, respectively. The elevated dioxin concentration with polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and coplanar-PCBs found in the fishermen may be due to the frequent consumption of fish; no such relationship was found both in the farmers and the controls. We found that the concentrations of congeners found as impurities in certain chemicals such as those previously used in agriculture showed no significant differences among the three groups; we consider it unlikely that the farmers would be directly exposed to dioxins from such chemicals. Thus, it is probable that the primary route of dioxin exposure in the Japanese population is through the food chain via fish consumption, regardless of occupation. No meaningful relationship between blood dioxin concentration and CYP1A1 polymorphisms was found in this study, although there was a significant difference between the concentration of total non-ortho-PCBs in genotypes A and B. Further studies on more subjects, including those of genotype C, are needed to confirm the relationship between blood dioxin concentrations and MspI polymorphisms.     

Removal of dioxins and related aromatic hydrocarbons from flue gas streams by adsorption and catalytic destruction

The dioxin removing capacity of the shell dedioxin system (SDDS-a Ti/V oxidative type catalyst) has been tested using the Ume? lab-scale incinerator over the temperature range 100-230 degrees C and at space velocities of 8000 and 40,000 h(-1). Other analogous organic compounds, such as PCBs, PAHs, chlorobenzenes and chlorophenols have also been investigated. Results show a high degree of dioxin removal already at 100 degrees C (82%), which occurs mainly by adsorption. When the temperature is raised a transition towards destruction is seen and at 150 degrees C, gas hour space velocity (GHSV) 8000 and at 230 degrees C, GHSV 40,000 virtually all removal is by destruction. High PCDD/F destruction efficiencies are reported (> 99.9%, based on I-TEQ); the other dioxin-related species and PAHs are also removed and destroyed to a significant extent. The SDDS has proved to be an effective means of destroying organic compounds in the gas phase, particularly dioxins, at temperatures as low as 150 degrees C.     

PCDD/F formation from oxy-PAH precursors in waste incinerator flyash

The yield of PCDD/F in relation to the presence of oxygenated PAH in model waste incinerator flyash has been investigated in a fixed bed laboratory scale reactor. Experiments were undertaken by thermal treatment of the model flyash at 250 and 350 °C under a simulated flue gas stream for 2 h. After reaction, the PCDD/F content of the reacted flyash and the PCDD/F released into the exhaust gas, and subsequently trapped by XAD-II resin in a down-stream condensation system were analyzed. The PAHs investigated were, dibenzofuran and benzo[b]naphtho[2,3-d]furan and were spiked onto the model flyash as reactant precursors for PCDD/F formation. The results showed significant formation of furans from both of the PAH investigated, however except from some highly chlorinated dioxin congeners, the formation of dioxins was not so common. Benzonaphthofuran was significantly more reactive than dibenzofuran in PCDD/F formation, in spite of the fact that dibenzofuran is structurally more similar to that of PCDD/F. Thus, there was no clear attribution between the chemical structure of PAH used and the formation of PCDD/F. There were considerable differences between the yields of PCDD/F congeners in the gaseous species and those in the reacted flyash under the same operational conditions. The concentration of PCDD/Fs was reduced at the higher reaction temperature of 350 °C; however, the higher temperature resulted in the majority of the PCDD/F formed on the flyash being released into the gas phase.     

Health risk assessment of dioxin emissions from municipal waste incinerators: the Neerlandquarter (Wilrijk, Belgium)

Two municipal waste incinerators in the vicinity of a residential area close to the city of Antwerp caused concern to local habitants. Risk assessment was performed combining chemical, toxicological measurements and model calculations. As the first step in risk assessment an inventory was made of historic emissions from both incinerators with emphasis on dioxins. The operational atmospheric transport and deposition model for priority substances (OPS) was used to calculate the deposition of dioxins in the vicinity of incinerators. The observed soil contamination pattern did not correspond to the calculated deposition pattern, indicating that other sources may contribute at least partly to the local PCDD/PCDF contamination of the area. Dioxin exposure of people in the Neerlandquarter as a function of the food consumption behavior was calculated using a mathematical model (VLIER-HUMAAN) combined with transfer factors. According to the results of these calculations, just residing in the impact area does not result in a meaningful risk. Only if locally produced food was consumed (milk, meat and vegetables), exposure in the Neerlandquarter was enhanced compared to the average dioxin exposure estimated for the Flemish population. Exposure in 1997 was below the exposure in 1980. As a consequence of different eating habits and lower bodyweight, children are subjected to significantly higher exposure than adults. Adverse health outcomes from dioxin exposure in the past cannot be excluded. There was no evidence for enhanced exposure to genotoxicants based on a comparison of chromosomal damage to blood cells of children from the study area to those from a control group.     

Formation of chlorinated and brominated dioxins and other organohalogen compounds at the pilot incineration plant VERONA

Experiments were conducted at the VERONA pilot plant, an incineration plant with stationary grate and separate post-combustion chamber, using wood and propane as basic combustible materials and with controlled dosage of various bromine-, chlorine- and copper-containing compounds. The behaviour of the following compounds was studied in the combustion chamber, after the post-combustion chamber and after the heat exchanger: polychlorinated phenols (PCPh), polybrominated phenols (PBrPh), polychlorinated benzenes (PCBz), polybrominated benzenes (PBrBz), polychlorinated dioxins and furans (PCDD/F) and polybrominated dioxins and furans (PBDD/F). The bromine co-incineration leaded to very high bromophenol concentrations after the post-combustion chamber. The formation of brominated and mixed-halogenated phenols and the further reaction to halogenated dioxins is apparently a relevant reaction mechanism for dioxin formation in processes involving bromine. This assumption is supported by the high formation rates of PBDD/F found in the heat exchanger, which were 4-20 times higher than those of PCDD/F. Moreover, the strong correlations found between the formation rates of PCPh, PCBz and PCDD/F in the heat exchanger indicate that in addition considerable new formation of dioxins takes place through de novo synthesis. Experiments involving the variation of primary operational parameters and fuel properties have shown that the quality of post-combustion plays a much greater role than the other parameters. Furthermore, it became apparent that the congeners of the chlorophenols and of the chlorobenzenes, measured in various incineration stages, do not correlate closely with the dioxin concentrations after the heat exchanger.     

The role of metals in dioxin formation from combustion of newspapers and polyvinyl chloride in an incinerator

Newspapers impregnated with NaCl mixed with various chloride metals (CuCl2, MgCl2, MnCl2, FeCl3, NiCl2, and CoCl2) and electric wire coated with polyvinyl chloride (PVC) were combusted in a well-controlled incinerator. Exhaust gas samples collected at the outlet of the incinerator were analyzed for dioxins (PCDDs, PCDFs, and coplanar PCBs) by gas chromatography/mass spectrometry. The amount of total dioxins formed from newspaper samples ranged from 34.2 ng/g (with NaCl+CoCl2) to 67.0 ng/g (with NaCl+CuCl2). PCDFs composed 88-94% of the total dioxins formed in the exhaust gases. The highest levels of PCDF isomers obtained were Cl3-CDF from the sample with NaCl+CuCl2 (14.8 ng/g), Cl2-CDF from the sample with NaCl+MgCl2 (12.3 ng/g), and Cl(1)-CDF from samples with NaCl+MnCl2 (12.6 ng/g), with NaCl+FeCl3 (11.8 ng/g), and with NaCl+NiCl2 (13.3 ng/g), and with NaCl+CoCl2 (8.62 ng/g). The total of Cl4-8-CDDs comprised 76-88% of the total Cl1-8-CDDs. In particular, Cl7-CDDs had the highest levels except for the sample with NaCl+NiCl2. Total dioxins formed from samples of electric wire coated with PVC and PVC alone were 38.3 ng/g and 112 ng/g, respectively, suggesting that the presence of copper reduced dioxin formation.     

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.     

The reduction of dioxin emissions from the processes of heat and power generation

The first reports that it is possible to emit dioxins from the heat and power generation sector are from the beginning of the 1980s. Detailed research proved that the emission of dioxins might occur during combustion of hard coal, brown coal, and furnace oil as well as coke-oven gas. The emission of dioxins occurs in wood incineration; wood that is clean and understood as biomass; or, in particular, wood waste (polluted). This paper thoroughly discusses the mechanism of dioxin formation in thermal processes, first and foremost in combustion processes. The parameters influencing the quantity of dioxins formed and the dependence of their quantity on the conditions of combustion are highlighted. Furthermore, the methods of reducing dioxin emissions from combustion processes (primary and secondary) are discussed. The most efficacious methods that may find application in the heat and power generation sector are proposed; this is relevant from the point of view of the implementation of the Stockholm Convention resolutions in Poland with regard to persistent organic pollutants.