Paper fibers as a carbon source for the de novo formation of polychlorinated dioxins and furans

The formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) from carbon that was produced by the pyrolysis of paper fibers and from wood charcoal was investigated experimentally. Fibers obtained from filter paper were pyrolyzed at 300° and 800°C to produce low- and high-temperature carbon samples. The two types of carbon and wood charcoal were mixed with silica (SiO₂) and trace copper oxide to produce three synthetic fly ash samples. Experiments to measure the formation of PCCDs/Fs from the three ash samples were conducted using a bench-scale reactor. The two carbon samples derived from paper fibers generated more PCDDs/Fs than was generated by the wood charcoal. The PCDDs/Fs generated by the low-temperature carbon and by the wood charcoal were dominated by the lower-chlorinated PCDFs. Such unique homologue distribution patterns are very similar to those generated by the open burning of household waste. The high-temperature carbon generated more highly chlorinated PCDDs/Fs. The effect of pyrolysis temperature on the de novo formation of PCDDs/Fs from residual carbon is discussed. Paper and paper products contained in household waste are likely to be the source of unburned carbon that contributes to high PCDD/F emissions in the open burning of household waste.     

Catalytic detoxification of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in fly ash

An efficient catalytic detoxification method for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in fly ash produced by municipal waste incinerator has been studied using palladium on carbon (Pd/C) catalyst. As one of the trace components in fly ash, the detoxification of PCDD/Fs is very difficult because of the interferences of other persistent components with higher concentrations. However, the detoxification reaction of PCDD/Fs shows higher activity in water/isopropanol solution using commercial Pd/C catalyst at 40 degrees C under normal pressure. The results indicated that the catalytic degradation of PCDFs has been found to be easier than that of PCDDs. Moreover, the dechlorination ratios were higher for octa- and hepta-chlorinated congeners than those for tetra- and penta-chlorinated ones. The detoxification process worked well in water. The dechlorination efficiencies of almost all of the PCDD/Fs congeners can reach over 99% within a shorter reaction time.     

Hydrodechlorination/detoxification of PCDDs,PCDFs, and co-PCBs in fly ash by using calcium polysulfide

Dioxins like polychlorinated dibenzo-p-dioxins (PCSDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are mainly emitted from waste incinerators (WIs) and have become an international research focus because of its serious concerns over the adverse health effects. The detoxification of PCCDs/Fs and PCBs is very difficult because of their stable chemical structure. A significant hydrodechlorination/detoxification of polychlorinated 1-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were achieved in fly ash by using an aqueous mixture of calcium hydroxide and sulfur. Two different fly ashes were studied: originating from municipal waste incinerator (FA1) and industrial waste incinerator (FA2). They were heated with the aqueous mixture at 150 °C for 30 or 60 min with agitation. Higher decomposition (87%) and detoxification (87.7%) of PCDD/Fs and PCBs were achieved at 150 °C with two runs; every run was for 30 min, compared to one run for 60 min. FA2 gave higher decomposition and detoxification as compared to FA1, which might be due to higher metal content that played a catalytic role to decompose and detoxify the PCDDs, PCDFs and PCBs. The decomposition and detoxification of PCDFs in fly ash was higher than PCDDs and was augmented with increasing number of chlorides on aromatic compounds. As the highly significant decomposition and detoxification of higher concentration of PCDD/Fs and PCBs were achieved in 1 hour without additive catalyst and at low temperature of 150 °C, therefore, the developed method is cost effective and most suitable to apply on commercial/industrial level. The detail results of hydrodechlorination/detoxification of PCDD, PCDFs at different conditions are described and its mechanism is discussed.     

Removal of carbon constituents from hospital solid waste incinerator fly ash by column flotation

Hospital solid waste incinerator (HSWI) fly ash contains a large number of carbon constituents including powder activated carbon and unburned carbon, which are the major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in fly ash. Therefore, the removal of carbon constituents could reduce PCDD/Fs in fly ash greatly. In this study, the effects of the main flotation parameters on the removal of carbon constituents were investigated, and the characteristics of the final product were evaluated. The results showed that loss on ignition (LOI) of fly ash increased from 11.1% to 31.6% during conditioning process. By optimizing the flotation parameters at slurry concentration 0.05 kg/l, kerosene dosage 12 kg/t, frother dosage 3 kg/t and air flow rate 0.06 m³/h, 92.7% of the carbon constituents were removed from the raw fly ash. Under these conditions, the froth product has LOI of 56.35% and calorific values of 12.5 MJ/kg, LOI in the tailings was below 5%, and the total toxic equivalent (TEQ) of PCDD/Fs decreased from 5.61 ng-TEQ/g in the raw fly ash to 1.47 ng-TEQ/g in the tailings. The results show that column flotation is a potential technology for simultaneous separation of carbon constituents and PCDD/Fs from HSWI fly ash.     

Indication of PCDD/F formation through precursor condensation in a full-scale hazardous waste incinerator

This paper gives the PCDD/F fingerprint of boiler and fly ash of a full scale hazardous waste incinerator and demonstrates that, when the waste to be incinerated contains high concentrations of PCBs and chlorinated pesticides, heterogeneous precursor condensation is the dominant PCDD/F formation mechanism rather than de novo synthesis. This is in contrast to full-scale municipal solid waste incinerators, where de novo synthesis has been shown to be the dominant PCDD/F formation mechanism. This paper agrees with earlier predictions based on numerous lab scale experiments.     

Sludge as dioxins suppressant in hospital waste incineration

Nitrogen containing compounds such as ammonia, urea and amines can effectively inhibit the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Sewage sludge accumulates both sulfur and nitrogen during wastewater treatment so it could be used to reduce PCDD/Fs formation. Indeed, it is observed in this study that the gas evolving from the sludge drying process can significantly suppress chlorobenzene (CBz) and PCDD/Fs formation from fly ash collected from a hospital waste incinerator. For instance, the reduction of hexachlorobenzene (HxCBz) and PCDD/Fs amount was 92.1% and 78.7%, respectively, when the drying gas evolving from 2g sludge flew through 2g fly ash. These tests were conducted in the frame of projects devoted to hospital waste incineration. The disposal technology for hospital waste (HW), developed in this institute, features rotary kiln pyrolysis combined with post-combustion followed by flue gas cleaning. Hence, some preliminary tests were devoted to investigate dioxins suppression by co-pyrolysis and co-combustion of polyvinyl chloride (PVC) and sludge in lab scale. More experimental research will be conducted to appropriately assess these effects of sludge on PCDD/Fs emissions during co-pyrolysis/combustion of HW and sludge.     

Repartition of PCDD and PCDF in the emissions of municipal solid waste incinerators between the particulate and volatile phases

The present paper refers to the results of a research project on the polychlorinated dibenzyil-p-dioxin (PCDD) and polychlorinated dibenzofurans repartition in particulate and volatile phase in emissions from municipal solid waste incinerators. The distribution of such micropollutants between the different phases is analyzed in terms of absolute weights and in terms of 2, 3, 7, 8 TCDD Equivalents. This paper shows that more than half of the total content of PCDD/Fs emitted are adsorbed in the fly ash, with the remaining part in the volatile phase. Such repartition is inverted if the PCDD/Fs are expressed in terms of 2, 3, 7, 8 TCDD Equivalent.     

Decreased PCDD/F formation when co-firing a waste fuel and biomass in a CFB boiler by addition of sulphates or municipal sewage sludge

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are formed during waste incineration and in waste-to-energy boilers. Incomplete combustion, too short residence times at low combustion temperatures (<700 °C), incineration of electronic waste and plastic waste containing chlorine are all factors influencing the formation of PCDD/Fs in boilers. The impact of chlorine and catalysing metals (such as copper and iron) in the fuel on PCDD/F formation was studied in a 12 MW_th circulating fluidised bed (CFB) boiler. The PCDD/F concentrations in the raw gas after the convection pass of the boiler and in the fly ashes were compared. The fuel types were a so-called clean biomass with low content of chlorine, biomass with enhanced content of chlorine from supply of PVC, and solid recovered fuel (SRF) which is a waste fuel containing higher concentrations of both chlorine, and catalysing metals. The PCDD/F formation increased for the biomass with enhanced chlorine content and it was significantly reduced in the raw gas as well as in the fly ashes by injection of ammonium sulphate. A link, the alkali chloride track, is demonstrated between the level of alkali chlorides in the gas phase, the chlorine content in the deposits in the convection pass and finally the PCDD/F formation. The formation of PCDD/Fs was also significantly reduced during co-combustion of SRF with municipal sewage sludge (MSS) compared to when SRF was fired without MSS as additional fuel.     

An investigation of halogens in Izmit hazardous and clinical waste incinerator

In the combustion facilities, halogens (Cl, F, Br, I) should be considered with regard to the control of the compounds such as polychlorinated dibenzodioxins (PCDD), polychlorinated dibenzofurans (PCDF), halogenated polyaromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB) and volatile heavy metals formed as a result of incomplete combustion and caused adverse environmental effects. In this study halogens were observed in Izmit Hazardous and Clinical Waste Incinerator (IZAYDAS). Halogen contents of the combustion menu, flue gas, fly ash, bottom ash and filter cake were measured and their distributions in these exit streams were determined. Results showed that the major part of the halogens was partitioned to solid residues, i.e., bottom ash and filter cake which represents the removal by wet scrubbers. Fly ash and flue gas fractions of halogens were much lower due to the reduced formation of volatile compounds.     

Effect of unburned carbon on lead, zinc, and copper recovery from molten fly ash by chloride-induced volatilization

The present work focuses on investigation of the effective recovery of heavy metals from molten fly ash by applying chloride-induced volatilization. In particular, the effect of unburned carbon on the chloride-induced volatilization of lead, zinc, and copper from model and real molten fly ashes was investigated in the temperature range 873–1173 K under a N₂ atmosphere. As a result, almost 100% of lead and a significant proportion of zinc were volatilized from the real molten fly ash samples at 1173 K. In contrast, for the model fly ash, volatilization ratios of lead and zinc at 1173 K were only 85% and 25%, respectively. Further, the results of X-ray diffraction analysis suggested that PbO in molten fly ash was converted either to Pb₂OCl₂ or Pb by respective chlorination and reduction reactions. Meanwhile ZnO and CuO in the molten fly ash were reduced to Zn and Cu by reaction with unburned carbon. Subsequently, Pb, Zn, and Pb₂OCl₂ were volatilized, but Cu remained in the solid residue. Finally, the volatilization ratio of zinc increased with the addition of carbon, and more than 98% of zinc was volatilized at 1173 K from a fly ash with a carbon content of 20%.     

Heavy metal speciation in various types of fly ash from municipal solid waste incinerator

Fly ash (FA) from municipal solid waste incinerators has been known as hazardous waste, which is mostly because of the high content of heavy metal and dioxins. Besides the content, the form of the heavy metals in fly ash is also very important, because it is tightly related with the leaching behavior of fly ash in diverse circumstances. To evaluate the environment potential risk of fly ash, the Tessier chemical extraction method was adopted. In this study, four kinds of fly ash were examined, one sample from China (CFA) and the other three from Japan (RFA, CaFA and NaFA). Five metal elements were detected and they were Ni, Cr, Cd, Pb, and Cu. The result of total heavy metals’ concentration showed CFA has the lowest content. As to the Tessier chemical extraction experiments, the results show that Cd, Pb, and Cu have higher leaching risk in the environment than other heavy metals. The result of leaching test experiment showed that the more exchangeable speciation of Cd, Cr and Pb in FA, the more it could leach out in natural environment.     

Persistent organic pollutant emissions from medical waste incinerators in China

The huge amount of medical waste (MW) has caused a tough challenge to environmental protection in China because of its serious infectious potential. At present, incineration is the most common technology for MW disposal. Unfortunately, the medical waste incinerator (MWI) is considered one of the major sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). This study was conducted to investigate the generation and the components of MW; the fingerprint of PCDD/Fs in MWI; and PCDD/F, polychlorinated biphenyl (PCB) and hexachlorobenzene concentrations in residue ash. The estimated annual production of MW was estimated to be 0.97 million tons in China in 2008; in addition, plastic and rubber accounted for 24.5% of MW contents. PCDD/F emissions from MWI could be divided into two main groups according their fingerprints, and the ratio of PCDFs/PCDDs was mostly over 1.5, with a mean value of 3.43. The toxic equivalent of PCDD/Fs was over 30 times that of the value of PCBs in the residue ash, and PCDD/F contents in fly ash accounted for approximately 67% of the total output of PCDD/Fs, which was in line with the UNEP default emission factors for MWI (class 3, 63.7%).     

An investigation on pollutant emissions from co-firing of RDF and coal

Pollutant emissions from co-firing of refuse derived fuel (RDF) and coal were investigated in a vortexing fluidized bed combustor (VFBC). RDF-5 was made of common municipal solid waste (MSW). CaCO₃ was injected in the combustor to absorb HCl at 850 °C. The results show that NO_x and HCl emissions increase with RDF-5 co-firing ratio. The NO_x concentration in flue gas at the bottom of the combustor is higher than that at the top. However, the trend of HCl released is reverse compared with NO_x emissions. It was found that the HCl concentration decreases with increasing the molar ratio of Ca/Cl. However, the effect of CaCO₃ addition on HCl retention is not significant when the molar ratio of Ca/Cl is higher than 5. The chlorine content in fly ash increases obviously with the molar ratio of Ca/Cl. PCDD/Fs emissions decrease slightly with an addition of CaCO₃. In this study incomplete combustion is regarded as the main cause for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) formation.     

Characterization of PCDD/Fs and heavy metals from MSW incineration plant in Harbin

The characterization of PCDD/Fs and heavy metals in the flue gas and fly ash of Harbin municipal solid waste (MSW) incineration plant, located in the northeast of China, was investigated in this study. The MSW was treated in a twin internal fluidized (TIF) bed incinerator. The results indicate that the emission of PCDD/Fs into the environment is 0.02 ng I-TEQ/m3 and the level of PCDD/Fs in the fabric filter fly ash is 0.7982 ng I-TEQ/g. The leachability levels of Pb, Cd and Hg in the fly ash are below the limits of environmental protection standard in China. However, the contents of Cu, Zn, and Hg are high in the fly ash. This suggests that the fly ash is a hazardous waste that requires special treatment and disposal. The practice of more than four years of operation shows that the TIF bed incinerator is very suitable and practical for China.     

Bench-scale studies on the simultaneous formation of PCBs and PCDD/Fs from combustion systems

The presence of endocrine disrupting chemicals (EDCs) in the environment has wide-ranging potential ecological and health impacts on animals and humans. A significant amount of experimental and theoretical work has been performed the examining formation and control of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), which account for only part of the EDCs being emitted from combustion devices. Generally accepted mechanistic theories for PCDD/F formation propose heterogeneous reactions in the cooler regions of the combustor involving gas-phase organic precursors (such as chlorobenzenes or chlorophenols), a chlorine donor [such as hydrogen chloride (HCl)], and a flyash-bound metallic catalyst (such as copper chloride). There is evidence that some other proposed EDCs, including polychlorinated biphenyls (PCBs), are formed through a similar mechanistic pathway as PCDD/Fs. In addition, there is evidence that certain important steps in the catalytic reaction between the copper catalyst and the organic precursors may suggest a common rate limiting step for the heterogeneous formation of the previously mentioned EDCs. This paper reports on a bench-scale experimental study to characterize a newly built reactor system that was built to: produce levels and distributions of PCDD/F production similar to those achieved by previous researchers; verify similar responses to changes in independent variables; examine the hypothesis that PCB formation rates exhibit trends similar to PCDD/F formation rates as reactor variables are changed; and begin to explore the dependence of PCB formation on temperature and precursor type. The reactor system has been built, and initial reactor characterization studies have been performed. Initial experiments yielded results that support the hypothesis of a similar formation mechanism of PCBs and PCDD/Fs in combustors. Initial experiments uncovered potential deficiencies with the reactor system and the experimental procedures and have suggested corrective action to improve the experimental system.     

Dechlorination/detoxification of aromatic chlorides using fly ash under mild conditions

An efficient dechlorination/detroxification method for p-nitrochlorobenzene, p-chloroanisole and 1-chloronaphthalene on municipal waste incinerator fly ash in presence of reducing agents with water/alcohol mixtures was developed. Dechlorination% was higher in water/isopropanol mixture at temperature <100 °C. Metal contents of fly ash played a vital role in enhancing dechlorination at low temperature. Moreover, the fly ash particles provided the surface to accomplish reduction and substitution reactions by adsorbing the chlorinated aromatic compound, hydrogen and hydroxyl ions. The mechanism of dechlorination was envisaged.     

Effects of combustion parameters on polychlorinated dibenzodioxin and dibenzofuran homologue profiles from municipal waste and coal co-combustion

Variation in polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran (PCDD and PCDF) homologue profiles from a pilot scale (0.6 MW_t, 2×10⁶ Btu/h), co-fired-fuel [densified refuse derived fuel (dRDF) and high-sulfur Illinois coal] combustion system was used to provide insights into effects of combustion parameters on PCDD and PCDF pollutant formation. A 24-run, statistically designed test matrix varied dRDF and/or coal firing rates (at a constant targeted energy release rate) along with a range of process variables including calcium hydroxide injection, hydrogen chloride (HCl) concentration, flue gas temperature, quench, and residence time such that the results would be relatable to a wide variety of combustion conditions. Statistical analysis of the molar homologue profiles enabled interpretation based on non-confounding variables. A multivariate, generalized additive model, based on transformations of the design variables, described 83% of the variation of the profiles characterized by log ratios of the homologue molar concentrations. This method identifies the operating parameters that are most significant in determining the PCDD/F homologue profiles. The model can be exercised to predict homologue profiles through input of these system-specific operating parameters. For example, both higher HCl and sulfur dioxide concentrations favor higher relative formation of the lower chlorinated PCDF homologues.     

Effects of fly ash addition on physical properties of porous clay-fly ash composites via polymeric replica technique

The porous composites of clay and fly ash have the potential to be used in many fields, such as catalyst support and gas adsorbents. In this study, various ratios of fly ash (1–2) with different percentage of suspension (50–70 wt%) were applied to produce porous clay-fly ash composites via polymeric replica technique. Fabrication process starts by mixing clay and fly ash in distilled water to form slurry. The process is followed by fully immersing polymer sponge in slurry. The excess slurry is then removed through squeezing. Finally, the sponge coated with slurry is sintered at 500 and 1250 °C for 1 h. It is found that the compressive strength of porous composites improves significantly (0.178–1.28 MPa) when the amount of clay-fly ash suspension mixture (50–70 wt%) increases. The compressive strength of porous composites is mainly attributed to the mullite, quartz and amorphous phase formations. These results are supported by X-ray diffraction analysis. On the other hand, increase in the amount of suspension reduces the apparent density (from 2.44 to 2.32 g/cm³) and porosity (from 97 to 85 %). The reduction in apparent density is believed to be caused by the presence of high fly ash content in porous composites. The melted fly ash cenospheres have closed the internal pores and increased density of samples. Higher suspension level not only reduces porosity, but also increases close pores of the porous composites. The results are justified through the observation from the structures of porous clay-fly ash composites.     

Statistical analysis as a tool for discriminating dioxin formation pathways

Typical thermal fingerprints are rather evenly composed of all available polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) congeners, a feature also linked with CuCl₂-catalysis. Conversely, chlorophenol condensation patterns are supported strongly by CrCl₃-, ZnCl₂- and CdCl₂-catalysis; they feature selective formation of, e.g., 1,3,6,8- and 1,3,7,9-TCDD arising from mainly 2,4,6-trichlorophenol, a chlorophenol well-represented in incinerator flue gas. Just few, well-defined PCDD-congeners steadily emerge from chlorophenols. Surprisingly, it is experimentally established that these are not generally formed by parallel processes. Additionally, the formation of four important 2,3,7,8-substituted TCDD/F- and PeCDD/F-congeners is statistically quasi-unrelated. Apparently, external (α) or lateral (β)-chlorination occurs as a chance event, contrary to observations and hypotheses in earlier studies. These statements are corroborated by selected congener-to-congener representations. For performing this statistical analysis, simple techniques are followed. Cross-correlation matrices show a relationship for each pair of PCDD/F-congeners in a particular data set: PCDD/F-congener pairs statistically correlate, anti-correlate, or appear rather neutral. In this paper, these novel concepts were applied on data, established during tests on Model Fly Ash (MFA); principal component analysis was used to demonstrate the relevance of MFA-data in relation to municipal solid waste incineration signatures.