Catalytic destruction of PCDD/F in a fabric filter: experience at a municipal waste incinerator in Belgium

In order to comply with dioxin and furan (PCDD/F) emission regulations in Belgium, the IVRO municipal waste incinerator adopted catalytic filters for use in the plant's two existing fabric filters. This system replaced the injection of powdered activated carbon (PAC) because of concerns that PAC, used at temperatures above 200 degrees C, would ignite and lead to fires and plant down-time. The performance of the catalytic filter system, since its installation in 1997, is described. PCDD/F emissions are controlled to well below the regulatory limit of 0.1 ng I-TEQ/Nm3. The amount of PCDD/F entering and exiting the fabric filter is quantified. The resulting mass balance shows that greater than 99.5% of the gaseous PCDD/F entering the fabric filter is destroyed by the catalyst within the filter media.     

Characterization and mass balance of dioxin from a large-scale municipal solid waste incinerator in China

The input and output samples from existing large-scale municipal solid waste incinerator (MSWI) were collected and analyzed for polychlorinated dibenzo-р-dioxins and dibenzofurans (PCDD/Fs) in this study, aiming to evaluate PCDD/F characteristic and the corresponding mass balance through the whole system. The grate-type MSWI is equipped with semi-dry scrubber, activated carbon injection, and bag filter as air pollutant control devices (APCDs). Results showed that on the output side, the stack gas, bottom ash and fly ash presented their mean dioxin levels of 0.078 ng I-TEQ/Nm(3), 12.94 ng I-TEQ/kg and 858 ng I-TEQ/kg, respectively, and showed large similarities in congener profiles. Instead, on the input side, the municipal solid waste (MSW) presented a mean dioxin level of 15.56 ng I-TEQ/kg and a remarkable difference in congener profiles compared with those of the output. The dioxin mass balance demonstrated that the annual dioxin input value was around 5.38 g I-TEQ/yr, lower than the total output value (7.62 g I-TEQ/yr), signifying a positive dioxin balance of about 2.25 g I-TEQ/yr.     

Semi-technical demonstration of the 3R process

The 3R Process: (1) recovers fly ash and HCl from the flue gases; (2) removes heavy metals from the fly ash by extraction with HCl; (3) and returns a pelletized fly ash to the incinerator. Recoveries of about 90% of the Cd, 65% of the Zn and 20% of the Pb and Cu have been achieved in pilot tests. Full scale experiments proved the thermal decomposition of PCDD/PCDF. The 3R products meet the Swiss elution requirements.     

Correlation study of hazardous waste characteristics among various chemical processes in Republic of Korea

To harmonize with international standards, the Republic of Korea is in the process of converting its current hazardous waste classification system and setting up regulatory standards for all toxic substances present in hazardous waste. Detailed characterization of each form of hazardous waste belonging to five chemical processes and their correlations were studied. In the present work, the concentrations of 13 heavy metals, F^?, CN^?, 7 PAH compounds, total PCDD/F and 7 PCB isomers present in the hazardous waste generated among chemical processes such as synthetic rubber (SR), man-made fibers (MF), organic dyes and pigments (DP), pharmaceuticals and cosmetics were analyzed along with their leaching characteristics. Comparing all the processes, most of the heavy metal concentrations were high in SR waste. Naphthalene was the dominant PAH in most of the chemical process waste. PCDD/F concentrations of the samples were in the range of 0.001–0.003 ng I-TEQ/g. PCB isomer-101 and isomer-118 were found to be slightly higher than the permissible limit in the SR filter cake sample. SR process wastes doesn’t show any resemblance with the other process waste in either the heavy metals and PAH trend. Each sample from DP and MF were suitable only for hazardous waste landfill.     

The New Jersey Toxics Reduction Workplan for Ny-Nj Harbor: Distribution of Pcdd/Fs in Ambient Waters

As part of the NJ Toxics Reduction Workplan for NY-NJ Harbor, ambient water samples were collected at fifteen locations along the tidal portions of the Hackensack, Passaic, Raritan, Rahway and Elizabeth Rivers, and in Newark Bay, the Arthur Kill, and Kill van Kull. A Trace Organics Platform Sampler was used to collect a total of 75 suspended sediment phase samples between June 2000 and May 2002. These samples were analyzed for spatial and wet vs. dry weather trends in the 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs; modified USEPA Method 1613b). Mean total PCDD/F (tPCDD/F) concentrations at the sampling locations ranged between 3.8 and 41.5 ng/g. On average, OCDD accounted for almost 80% of the tPCDD/F concentrations; mean total [PCDD/F – OCDD] concentrations ranged between 0.84 and 5.20 ng/g at the sampling locations. Mean 2,3,7,8-TCDD concentrations ranged between 0.003 and 0.28 ng/g, with the highest concentrations (> 0.10 ng/g) along the tidal Passaic and lower Hackensack Rivers, and in upper Newark Bay. Mean tPCDD/F Toxic Equivalency Quotients (TEQ) ranged between 45 and 344 TEQ pg/g, with the highest levels found in the lower Passaic River. Toxicity was primarily driven by 2,3,7,8-TCDD concentrations in the Passaic and Hackensack Rivers, and in Newark Bay. Examples of congener distribution patterns at some of the sampling locations are also presented.     

Dioxin emissions from thermal waste management in Medellín, Colombia: present regulation status and preliminary results

Preliminary results of a study undertaken to characterize dioxin and furan releases from waste incineration plants operating in Medellín-Colombia are presented. Emission and fly ash samples were collected from representative plants burning medical and industrial residues to characterize PCDD/PCDF levels. Analyses were carried out following European standards for stationary gas emissions EN-1948:1996 and US EPA 1613 (fly ashes). Final extracts were analyzed by both high resolution gas chromatography coupled to high resolution mass spectrometry (HRGC-HRMS) and high resolution gas chromatography coupled to ion trap tandem mass spectrometry (HRGC-ITMS/MS). Preliminary results revealed emission levels of 1-30.3 ng I-TEQ/Nm3 depending on whether or not an air pollution control system (APCS) was installed. Fly ashes contained 8.5-68 ng I-TEQ/g. Critical issues that should be addressed in an assessment and in developing waste management plans in Colombia are discussed.     

SETTING DIOXIN EMISSION LIMITS FOR MSW INCINERATORS: A MULTIMEDIA EXPOSURE ASSESSMENT FRAMEWORK

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are emitted in trace amounts from municipal solid waste (MSW) incinerators. The exposure to PCDD/Fs experienced by an individual is dominated by the food chain pathway, which accounts for over 98% of the total uptake. Defining a target daily intake (the World Health Organization TDI of 10 pg I-TEQ kg.bw⁻¹day⁻¹) exposure assessment algorithms were then applied to arrive at the corresponding PCDD/F levels in air, soil, plants, food products, etc., which would allow the target intake to be met while retaining the balance of intake between the various exposure pathways. These concentrations were converted to an ambient air concentration of PCDD/Fs and ultimately, by defining criteria for acceptability, to a guide value for PCDD/F concentration in emissions from the MSW incinerator. This strategy was applied to PCDD/F emissions from MSW incinerators of various sizes against two illustrative criteria for acceptability: an “insignificant” release and a threshold above which the release may require further assessment for environmental effects and for control. Using the criteria developed in this paper, the current PCDD/F emission limit of 0.1 ng I-TEQ m⁻³results in an emission that is classed as “insignificant” for all plant sizes. However, higher emission concentrations can also be accommodated below the threshold for further assessment and control.     

Verification results of jet resonance-enhanced multiphoton ionization as a real-time PCDD/F emission monitor

A jet resonance-enhanced multiphoton ionization (REMPI) monitor was tested on a hazardous-waste-fired boiler for its ability to determine concentrations of polychlorinated dibenzodioxins and dibenzofurans (PCDDs/Fs). Jet REMPI is a real-time instrument capable of highly selective and sensitive (from parts per billion to parts per trillion) detection of a broad range of aromatic compounds, including a number of air toxic compounds. The PCDD/F toxic equivalency (TEQ) value was derived from a predetermined correlation (R ² = 0.74) with monochlorobenzene (MClBz). This relationship was applied to nine subsequent jet REMPI on-line measurements of MClBz and parallel, standard extractive sampling for PCDD/F TEQ. For high waste-firing rates, with a range of PCDD/F TEQ values between 3.9 and 6.0 ng TEQ/m³, the TEQ values predicted by jet REMPI had a relative difference of 26% with the standard EPA Method 23 results. At low waste-firing rates (0.9–1.6 ng TEQ/m³), the relative difference increased to 219%. This limited testing shows that jet REMPI has promise as an on-line diagnostic monitor, providing feedback on the effects on PCDD/F emissions of operating parameter changes such as fuel feed interruptions or air pollution control failures.     

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.     

Emissions of organic micropollutants from discontinuously operated municipal waste incinerators

The emission of particles and organic micropollutants (PAH, PCDD and PCDF) was measured from three intermittently operated municipal waste incinerators of medium size. The mutagenicity of the stack gas samples were measured as well. The results show a good agreement between the PAH emitted and the mutagenicity in the stack gases, but none of these parameters correlate with the PCDD/PCDF content.     

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.     

Environmental Technology Verification (ETV) test of dioxin emission monitors

The performance of four dioxin emission monitors, including two long-term sampling devices, the Dioxin-MonitoringSystem (DMS) and AMESA (the adsorption method for sampling dioxins and furans), and two semireal-time continuous monitors, the resonance ionization with multimirror photon accumulation time-of-flight mass spectrometer (RIMMPA-TOFMS) and the jet resonance-enhanced multiphoton ionization (jet-REMPI) system were tested. A package boiler burning a simulated chlorinated hazardous waste was used for a total of nine tests. Reference samples were collected during each test and analyzed for polychlorinated dibenzodioxins and dibenzofurans (PCDDs/Fs) using gas chromatography mass spectrometry. The PCDD/F concentrations of the reference samples measured by EPA Method 23 ranged from 0.9 to 6.0 ng toxic equivalence (TEQ)/dry standard cubic meter. The relative accuracies achieved by DMS, AMESA, and jet-REMPI varied from 22.6% to 78.2%, with 100% data completeness. The RIMMPA-TOFMS produced no quantifiable results due to various difficulties associated with the instrument during the testing. The two long-term samplers were easy to install and operate and provided a cumulative, averaged emission for the sampling period. The operations of the two semi-real-time continuous monitors were relatively complex, but one of them provided on-site, real-time data for PCDD/F emissions from measurement of a TEQ correlative indicator compound. This article summarizes results from the individual Environmental Technology Verification reports for the four dioxin monitors. This work was presented, in part, at the Fourth International Conference on Combustion, Incineration/Pyrolysis and Emission Control (i-CIPEC)     

PCBs,PBDEs and dioxin-related compounds in floor dust from an informal end-of-life vehicle recycling site in northern Vietnam: contamination levels and implications for human exposure

Floor dusts from Vietnamese end-of-life vehicle (ELV)-processing households were investigated to elucidate the contamination levels and exposure risk of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and dioxin-related compounds (DRCs). The concentrations were in order of PBDEs (260–11,000, median 280 ng/g overall) > PCBs (19–2200, median 140 ng/g) > dioxin-like PCBs (8.8–450, median 22 ng/g) ? polybrominated dibenzo-p-dioxin/dibenzofurans (PBDD/Fs, 2000–28,000, median 8500 pg/g) > polychlorinated dibenzo-p-dioxin/dibenzofurans (PCDD/Fs, 440–4100, median 1800 pg/g) > MoBPCDD/Fs (1.9–1200, median 250 pg/g). Concentrations of PCBs and DRCs were higher than those reported for Vietnamese urban houses, indicating ELV processing as a significant source of these contaminants. Higher concentrations of PCBs relative to PBDEs suggest the abundance of old electrical capacitors/transformers in ELVs. The PBDD/F and PCDD/F profiles were indicative of DecaBDE-containing materials and combustion sources, respectively. PBDFs, PCDFs and DL-PCBs were the most important dioxin-like toxic equivalent (TEQ) contributors. The estimated PCB and TEQ intake doses from dust ingestion approached or exceeded the reference doses for children living in some ELV-processing households, indicating potential health risk. More comprehensive risk assessment of the exposure to PCBs and DRCs is required for residents of informal ELV recycling sites.     

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.     

Treatment of tar pond sludge in a circulating fluidized bed combustor

A series of tests to burn mixtures of tar pond sludge and coal was carried out using a mini‐circulating fluidized bed combustor (mini‐CFBC). During the tests, carbon dioxide, oxygen, carbon monoxide, sulfur dioxide, and nitrogen oxides in the flue gas were monitored continuously. Stack gas sampling was carried out for hydrochloric acid, metals, particulate matter, volatile organic compounds (VOCs), total hydrocarbons, semivolatile organic compounds (SVOCs), dioxins and furans (PCDD/Fs), and polychlorinated biphenyls (PCBs). Results showed that hydrochloric acid, mercury, particulate matter, PCDD/F, and metal concentrations were all below both the current limits and the gas‐release limits to be implemented in 2008 in Canada. The new 2008 emissions limits will reduce the maximum allowable concentrations of most pollutants by half. Thus, the maximum concentration for particulate matter will be 5 mg/m³ (from the current maximum concentration of 10 mg/m³);the maximum concentration for hydrochloric acid will be 5 mg/m³ (from 10 mg/m³); and the‐maximum concentration for dioxins and furans will be 0.032 ng/m toxic equivalent (from 0.08 ng/mcurrently). Sulfur capture efficiency was 89–91 percent. The percentage of fuel nitrogen converted to nitrogen oxides was of the order of 4.7 to 6.1, which is significantly lower than that of conventional pulverized coal‐fired boilers and well within the normal range for fluidized bed combustors (FBCs). PCB and polycyclic aromatic hydrocarbon (PAH) emissions levels were comparable or lower than levels reported in the literature for industrial‐scale FBCs. VOC concentrations were low except for benzene, for which the concentration was higher than that reported for pulverized coal‐fired utility boilers. In addition, carbon monoxide concentration was high at 1,200 to 2,200 parts per million. However, these carbon monoxide concentrations are typical of the mini‐CFBC firing coal. The trials showed that for 10 percent by weight tar pond sludge mixed with 90 percent by weight coal, the combustion was both stable and efficient. The tests demonstrated that CFBC technology is an environmentally sound option for eliminating tar pond waste sludge. © 2005 Wiley Periodicals, Inc.     

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.     

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%).     

Effects of gaseous NH(3) and SO(2) on the concentration profiles of PCDD/F in flyash under post-combustion zone conditions

The influence of gaseous ammonia and sulphur dioxide on the formation of 2378-substituted PCDD/F on a reference flyash from a municipal waste incinerator has been investigated using a laboratory scale fixed-bed reactor. The reference flyash samples (BCR-490) was reacted under a simulated flue gas stream at temperatures of 225 and 375°C for 96h. The experiments were carried out in two series: first with simulated flue gas alone, and then with injection of NH(3) or SO(2) gas into the flue gas just before the reactor inlet. It was found that the injection of gaseous ammonia into the flue gas could decrease the concentration of both PCDD and PCDF by 34-75% from the solid phase and by 21-40% from the gas phase. Converting the results to I-TEQ values, it could reduce the total I-TEQ values of PCDD and PCDF in the sum of the flyash and exhaust flue gas by 42-75% and 24-57% respectively. The application of SO(2) led to 99% and 93% reductions in the PCDD and PCDF average congener concentrations, respectively in the solid phase. In the gas phase, the total reductions were 89% and 76% for PCDD and PCDF, respectively. Moreover, addition of SO(2) reduced the total I-TEQ value of PCDD and PCDF in the flyash and exhaust flue gas together by 60-86% and 72-82% respectively. Sulphur dioxide was more effective than ammonia in suppressing PCDD/F formation in flyash under the conditions investigated.     

Influences of chlorine content on emission of HCl and organic compounds in waste incineration using fluidized beds

HCl and some organic compounds are the precursors of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) in municipal solid waste incinerators. In this work, a lab-scale fluidized bed incinerator is adopted to study the relationship between the organic and the inorganic chlorine contents of artificial wastes and the emissions of HCl and organic compounds. The lower threshold limit (LTL) of chlorine content below which HCl and organic compounds are not generated is studied. Experimental results showed that organic chlorides had a greater potential to release chlorine than inorganic chlorides. The generation of organic pollutants fell, but the emissions of HCl increased with the temperature. The concentrations of chlorophenols (CPs)/chlorobenzenes (CBs) increased with chlorine contents. No LTL existed for HCl regardless of whether CaO was added. The LTL for CPs was between 0.1 and 0.3wt% of inorganic chloride, but there was none for organic sources. For CBs, the LTL was between 0.5 and 1.0wt% for inorganics at 700 and 800 degrees C, but 0.1-0.3 wt% at 700 degrees C and 0.3-0.5 wt% at 800 degrees C for organics. The production of PAHs and benzene, toluene, ethylbenzene and xylene (BTEX) was related to the surplus hydrogen ions that were not reacted with the chlorine. Adding CaO inhibited the production of HCl, CBs and CPs, but did not seriously affect PAHs and BTEX.