Study of PCDD/Fs distribution in fly ash,ash deposits,and bottom ash from a medical waste incinerator in China

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.     

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.     

Effect of urea on fly ash PCDD/F concentrations in different particle sizes

The effect of urea as an inhibitor for reducing polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) concentrations in flue gases was studied in a pilot scale plant, together with the effect on the particle size distribution of these compounds. Total PCDD/F concentrations decreased by a maximum of 74%, the decrease being greatest for the most highly (octa-) chlorinated isomers. The PCDD/F reduction affected all the particle size classes when an adequate amount of urea was used (1% of the fuel input), which indicates that inhibition, unlike formation, is independent of the fly ash particle size distribution.     

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.     

Suppressing effect of goethite on PCDD/F and HCB emissions from plastic materials incineration

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.     

Assessment of the PCDD/F fate from MSWI residue used in road construction in France

MSWI fly ash is susceptible to contain high amount of polychlorinated dibenzo-dioxins and polychlorinated dibenzo-furans. However, the use of MSWI residue for road construction started in France at a period when MSWI Bottom Ash and MSWI fly ash were not separated. From four old road sites, MSWI residue, road soils, reference soils and geo-textiles were sampled and their PCDD/F contents were analyzed. MSWI residue show a great heterogeneity but also high amounts of PCDD/F (14-2960 ng I-TEQ kg(-1)dm). Soils underlying the road show less heterogeneity and PCDD/F contents between 0.57 and 7.23 ng I-TEQ kg(-1)dm, lower than ordinary soils. Moreover, the specific analysis of the 17 toxic PCDD/F congeners (notably the 2,3,7,8-TetraCDD) indicates the very low harmfulness of road soils. The study also allows to assert the relation between the MSWI residue particle size and the PCDD/F content.     

流化床垃圾焚烧炉产生的有毒二噁英同类物分布研究

测定了流化床垃圾焚烧炉焚烧产生的飞灰、烟尘和烟气中的2，3，7，8位氯取代二噁英同类物的含量及其毒性当量。结果表明，产生的二噁英主要存在于飞灰中，烟气中的含量很少。飞灰中二噁英总浓度和毒性当量分别为8.44ng／g和0．80ng／g，经过布袋除尘器后的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为0．34ng／m^3和0．02ng／m^3，而布袋除尘器前的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为40．78ng／m^3和3．0ng／m^3。飞灰和烟尘中2，3，7，8位氯取代二噁英同类物的分布相似，但是与烟气中2，3，7，8位氯取代二噁英同类物的分布差别较大。通过了解有毒二噁英同类物的分布，可以进一步优化流化床垃圾焚烧炉的焚烧条件，降低二噁英的排放量，减少垃圾焚烧对环境的污染。     

Dechlorination of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans on fly ash

Dechlorination of commercial mixtures of polychlorinated biphenyls (PCB) as well as polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) on extracted and non-extracted fly ash obtained from municipal waste incinerator (MWI) was studied in closed systems under nitrogen atmosphere at temperatures of 260°C and 340°C. Decomposition results (given as the difference between PCB or PCDD/F molar amounts before and after the experiment (in %) due predominantly to dechlorination reactions) and detoxification data (expressed similarly but related to toxic PCB and PCDD/F congeners only and given in I-TEQ units) are reported. Detoxification of Delor 105/80T at 260°C and 340°C at a loading of 0.65 wt% was 99.48% and 100%, respectively. The decomposition of Delor 103 at 340°C and for the loading of 0.75 wt% corresponded to 99.99%. The detoxification capability of PCDD/Fs on extracted and non-extracted fly ash for loading of 130 and 264 ng/0.4 g of fly ash at 340°C made 96 and 98%, respectively.     

The behavior of PCDD and PCDF during thermal treatment of waste incineration ash

The polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) content of three fly ash samples with different elemental compositions from different municipal waste incinerators were analyzed before and after thermal treatment at 300 °C or 500 °C. Gas phase emissions during the treatments were also collected and analyzed. Substantial reductions in the total PCCD/F content of the ashes were observed after treatment at 500 °C, seemingly due to degradation rather than dechlorination. Treatment at 300 °C resulted in an increase in the PCDD/F content of the three ashes. Initial concentration of PCDD/F in the untreated ashes did not reflect the outcome of the treatment at the different temperatures. In addition, the composition of the ash was found to influence the rate of decomposition and formation of PCDD and PCDF during thermal treatment; the results showed that Cu, Fe, Ca and S play important roles in these processes.     

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.     

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.     

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.     

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.     

Fate of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans in a Fly Ash Treatment Plant

Abstract

To understand the fate of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in a fly ash treatment plant that used the Waelz rotary kiln process (hereafter the Waelz process), the samples of input and output media were collected and analyzed. The most important PCDD/F source in input mass was electric arc furnace (EAF) fly ash, which had a mean PCDD/F content of 18.51 ng/g and contributed more than 99% of PCDD/F input mass, whereas the PCDD/F input mass fractions contributed by the coke, sand, and ambient air were only 0.04%, 0.02%, and 0.000002%, respectively. For the PCDD/F output mass in the Waelz process, the major total PCDD/F contents of 43.73 and 10.78 ng/g were in bag-filter and cyclone ashes, which accounted for approximately 69% and 17%, respectively, whereas those of stack flue gas and slag were 14% and 0.423%, respectively. The Waelz process has a dechlorination mechanism for higher chlorinated congeners, but it is difficult to decompose the aromatic rings of PCDD/Fs. Therefore, this resulted in the accumulation of lower chlorinated congeners. The output/input ratio of total PCDD/F mass and total PCDD/F international toxicity equivalence (I-TEQ) was 0.62 and 1.19, respectively. Thus, the Waelz process for the depletion effect of total PCDD/F mass was positive but minor, whereas the effect for total PCDD/F I-TEQ was adverse overall.     

Fate of polychlorinated dibenzo-p-dioxins and dibenzofurans in a fly ash treatment plant

To understand the fate of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in a fly ash treatment plant that used the Waelz rotary kiln process (hereafter the Waelz process), the samples of input and output media were collected and analyzed. The most important PCDD/F source in input mass was electric arc furnace (EAF) fly ash, which had a mean PCDD/F content of 18.51 ng/g and contributed more than 99% of PCDD/F input mass, whereas the PCDD/F input mass fractions contributed by the coke, sand, and ambient air were only 0.04%, 0.02%, and 0.000002%, respectively. For the PCDD/F output mass in the Waelz process, the major total PCDD/F contents of 43.73 and 10.78 ng/g were in bag-filter and cyclone ashes, which accounted for approximately 69% and 17%, respectively, whereas those of stack flue gas and slag were 14% and 0.423%, respectively. The Waelz process has a dechlorination mechanism for higher chlorinated congeners, but it is difficult to decompose the aromatic rings of PCDD/Fs. Therefore, this resulted in the accumulation of lower chlorinated congeners. The output/input ratio of total PCDD/F mass and total PCDD/F international toxicity equivalence (I-TEQ) was 0.62 and 1.19, respectively. Thus, the Waelz process for the depletion effect of total PCDD/F mass was positive but minor, whereas the effect for total PCDD/F I-TEQ was adverse overall.     

Formation of aromatic chlorinated compounds catalyzed by copper and iron

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.     

Chemical kinetic modeling of de novo synthesis of PCDD/F in municipal waste incinerators

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.     

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.     

Dioxins/furans emissions from fluidized bed combustion of salt-laden hog fuel

Polychlorinated dibenzodioxins/furans (PCDD/F) were formed in substantial quantities in a pilot-scale fluidized bed combustor burning salt-laden waste wood, a common fuel for Canadian coastal pulp and paper mills. Formation of PCDD/F increased with increasing chloride content in the feed, and appeared to correlate with the chlorine content in the fly ash. It took a very long time for the ash chlorine content to stabilize, suggesting that chlorine transferred slowly from the flue gas to the ash. The baghouse may contribute largely to formation of the PCDD/F, owing to its temperature range and the potentially long residence time for ash particles. Controlling the baghouse temperature to reduce the PCDD/F formation in the baghouse should be effective in reducing the total emission level. While sulphur addition was found to reduce the emission level by as much as 90%, the emission level was still above the regulated level for the mills burning salt-laden wood under the conditions of the present study. No relation between the emission level and CO concentration in the flue gas was observed.     

Effects of selected metal oxides on the dechlorination and destruction of PCDD and PCDF

OCDD and OCDF spiked silica/graphite based model fly ash containing various copper compounds and metal oxides were thermally treated under oxygen deficient conditions. All copper compounds tested showed a considerable dechlorination/hydrogenation reaction at 260 °C. After 30 min at 340 °C, less than 1% of the spiked OCDD and OCDF was recovered as T₄CDD/F to OCDD/F. Other compounds tested demonstrated a lower rate of dechlorination compared to the copper compounds. However, all other metal oxides showed a small dechlorination effect at 260 °C, which was considerably increased at 340 °C.

The model fly ash containing the different copper compounds or metal oxides showed comparable PCDD and PCDF isomer patterns after thermal treatment. However, small differences were observed among the different tested compounds. The PCDD and PCDF isomer patterns on the model fly ashes were similar to patterns found during dechlorination experiments on fly ashes from waste incineration processes.

Model fly ash containing Ca(OH)₂ exhibited the highest destruction potential, but a low dechlorination potential. In contrast, model fly ash containing any of the remaining compounds tested, was found to predominantly dechlorinate the spiked OCDD and OCDF.