The prediction of PCDD/DF levels in wet scrubbers associated with waste incinerators

Wet scrubber is one of the most conventional types of air pollutant control devices (APCDs), which is specially designed to treat dust and acidic gases in the flue gas simultaneously. In spite of its outstanding ability to control them, however, wet scrubbers have been considered as potential contaminant sources that may increase PCDD/DF concentrations in the flue gas. In this study, we investigated the change of PCDD/DF concentrations at the inlets and outlets of seven wet scrubbers, and compared them with other published data. With a multi-regression analysis of dust concentrations and temperature at the inlets and outlets of given wet scrubbers, we developed an empirical model to understand factors dominating the change of PCDD/DF concentrations. As a result, we confirmed that the changes of PCDD/DF concentrations in wet scrubbers are closely related to their concentrations at the inlets, which would usually be determined by the type of APCDs installed upstream of the wet scrubber.     

Assessment of emissions and removal of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) at start-up periods in a hazardous waste incinerator

A study was conducted to observe the changes in polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) levels and congener profiles in the flue gas of a hazardous waste incinerator during two start-up periods. Flue gas samplings were performed simultaneously through Air Pollution Control Devices (APCDs) (including boiler outlet, electrostatic precipitator (ESP) outlet, wet scrubbers (WS) outlet, and activated carbon (AC) filter outlet) in different combustion temperatures during a planned cold (long) start-up and an unplanned warm (short) start-up. The results showed that PCDD/F concentrations could be elevated during the start-up periods up to levels 3–4 times higher than those observed in the normal operation. Especially lower combustion temperatures in the short start-ups may cause high PCDD/F concentrations in the raw flue gas. Assessment of combustion temperatures and Furans/Dioxins values indicated that surface-catalyzed de novo synthesis was the dominant pathway in the formation of PCDD/Fs in the combustion units. PCDD/F removal efficiencies of Air Pollution Control Devices suggested that formation by de novo synthesis existed in ESP also when in operation, leading to increase of gaseous phase PCDD/Fs in ESP. Particle-bound PCDD/Fs were removed mainly by ESP and WS, while gaseous phase PCDD/Fs were removed by WS, and more efficiently by AC filter.

Implications: This paper evaluates PCDD/F emissions and removal performances of APCDs (ESP, wet scrubbers, and activated carbon) during two start-up periods in an incinerator. The main implications are the following: (1) start-up periods increase PCDD/F emissions up to 2–3 times in the incinerator; (2) low combustion temperatures in start-ups cause high PCDD/F emissions in raw gas; (3) formation of PCDD/Fs by de novo synthesis occurs in ESP; (4) AC is efficient in removing gaseous PCDD/Fs, but may increase particle-bound ones; and (5) scrubbers remove both gaseous and particle-bound PCDD/Fs efficiently.     

Evaluation of PCDD/F congener distributions in MWI flue gas treated with SCR catalysts

Partitioning of PCDD/F congeners between gaseous and particulate phases and removal efficiencies of the air pollution control devices (APCDs) for PCDD/Fs at an existing municipal waste incinerator (MWI) in Taiwan are evaluated via stack sampling and analysis. The MWI investigated is equipped with electrostatic precipitators (EP), wet scrubbers (WS) and selective catalytic reduction system (SCR) as APCDs. The average PCDD/F concentration of stack gas is 1.49 ng/N m³, and the International Toxic Equivalent Quantity (I-TEQ) is 0.043 ng-I-TEQ/N m³. The EP increases PCDD/F concentration by 174.0% while the average removal efficiency of WS + SCR system for PCDD/Fs reaches 99.1%. In addition, the PCDF removal efficiency achieved with WS + SCR system (97.1–99.8%) is higher than that for PCDDs (96.5–99.3%). The results obtained on gas/particulate partitioning in flue gas indicate that the particulate-phase PCDD/Fs accounted for 65% at the inlet of EP, 20% at the outlet of EP and 50% at the stack, respectively, of the total PCDD/F concentrations. This study also indicates that as the chlorination level of PCDD/F congeners increases, the percentage of PCDD/Fs existing in gas phase decreases in all flue gas samples.     

Formation and removal of PCDD/Fs in a municipal waste incinerator during different operating periods

The PCDD/F concentrations and removal efficiencies achieved with air pollution control devices (APCDs) during different operating periods (start-up, normal operation, and shut-down) at an existing municipal waste incinerator (MWI) in Taiwan are evaluated via stack sampling and analysis. The MWI investigated is equipped with electrostatic precipitators (EP), wet scrubbers (WS), and selective catalytic reduction system (SCR) as APCDs. The sampling results indicate that the PCDD/F concentrations at the EP inlet during start-up period were 15 times higher than that measured during normal operation period. The PCDD/F concentration observed at shut-down period was close to that measured at normal operation period. The CO concentration was between 400 and 1000 ppm during start-up period, which was about 50 times higher compared with the normal operation. Hence, combustion condition significantly affected the PCDD/F formation concentration during the waste incineration process. In addition, the distributions of the PCDD/F congeners were similar at different operating periods. During the normal operation and shut-down periods, the EP decreases the PCDD/F concentration (based on TEQ) by 18.4-48.6%, while the removal efficiency of PCDD/Fs achieved with SCR system reaches 99.3-99.6%. Nevertheless, the PCDD/F removal efficiency achieved with SCR was only 42% during the 19-h start-up period due to the low SCR operating temperature (195 degrees C).     

Evaluating the performance of a turbulent wet scrubber for scrubbing particulate matter

A turbulent wet scrubber was designed and developed to scrub particulate matter (PM) at micrometer and submicrometer levels from the effluent gas stream of an industrial coal furnace. Experiments were conducted to estimate the particle removal efficiency of the turbulent scrubber with different gas flow rates and liquid heads above the nozzle. Particles larger than 1 µm were removed very efficiently, at nearly 100%, depending upon the flow rate, the concentration of the dust-laden air stream, and the water level in the reservoir. Particles smaller than 1 µm were also removed to a greater extent at higher gas flow rates and for greater liquid heads. Pressure-drop studies were also carried out to estimate the energy consumed by the scrubber for the entire range of particle sizes distributed in the carrier gas. A maximum pressure drop of 217 mm H₂O was observed for a liquid head of 36 cm and a gas flow rate of 7 m³/min. The number of transfer units (NTU) analysis for the efficiencies achieved by the turbulent scrubber over the range of particles also reveals that the contacting power achieved by the scrubber is better except for smaller particles. The turbulent scrubber is more competent for scrubbing particulate matter, in particular PM_2.5, than other higher energy or conventional scrubbers, and is comparable to other wet scrubbers of its kind for the amount of energy spent.

Implications: The evaluation of the turbulent scrubber is done to add a novel scrubber in the list of wet scrubbers for industrial applications, yet simple in design, easy to operate, with better compactness, and with high efficiencies at lower energy consumption. Hence the turbulent scrubber can be used to combat particulate from industrial gaseous effluents and also has a scope to absorb gaseous pollutants if the gases are soluble in the medium used for particles capture.     

Destruction of PCDD/Fs by SCR from flue gases of municipal waste incinerator and metal smelting plant

Partitioning of PCDD/F congeners between vapor/solid phases and removal and destruction efficiencies achieved with selective catalytic reduction (SCR) system for PCDD/Fs at an existing municipal waste incinerator (MWI) and metal smelting plant (MSP) in Taiwan are evaluated via stack sampling and analysis. The MWI investigated is equipped with electrostatic precipitators (EP, operating temperature: 230 degrees C), wet scrubbers (WS, operating temperature: 70 degrees C) and SCR (operating temperature: 220 degrees C) as major air pollution control devices (APCDs). PCDD/F concentration measured at stack gas of the MWI investigated is 0.728 ng-TEQ/Nm(3). The removal efficiency of WS+SCR system for PCDD/Fs reaches 93% in the MWI investigated. The MSP investigated is equipped with EP (operating temperature: 240 degrees C) and SCR (operating temperature: 290 degrees C) as APCDs. The flue gas sampling results also indicate that PCDD/F concentration treated with SCR is 1.35 ng-TEQ/Nm(3). The SCR system adopted in MSP can remove 52.3% PCDD/Fs from flue gases (SCR operating temperature: 290 degrees C, Gas flow rate: 660 kN m(3)/h). In addition, the distributions of PCDD/F congeners observed in the flue gases of the MWI and MSP investigated are significantly different. This study also indicates that the PCDD/F congeners measured in the flue gases of those two facilities are mostly distributed in vapor phase prior to the SCR system and shift to solid phase (vapor-phase PCDD/Fs are effectively decomposed) after being treated with catalyst. Besides, the results also indicate that with SCR highly chlorinated PCDD/F congeners can be transformed to lowly chlorinated PCDD/F congeners probably by dechlorination, while the removal efficiencies of vapor-phase PCDD/Fs increase with increasing chlorination.     

PCDD/DF in leachates from Korean MSW landfills

We analyzed levels of PCDD/DF in leachate liquid and solid from five Korean municipal solid waste landfills to investigate the relationship between PCDD/DF and dissolved organic carbon and suspended solids in raw leachate. The concentrations of PCDD/DF ranged from 173.2 to 1329.4 pg/l and 4.1 to 46.22 pg-TEQ/l. The range of PCDD/DF was 123.2-1161.3 pg/l in leachate solid and 50.0-383.3 pg/l in leachate liquid. Our results indicated that PCDD/DF in solid play a major role in determining their concentration levels, and the distribution of isomers in solid was almost the same as in liquid leachate. In addition, highly chlorinated PCDD/DF, such as HpCDD/DF and OCDD/DF, accounted for more than 70% of all isomers. Levels of PCDD/DF in liquid were strongly correlated with dissolved organic carbon concentrations, which increase the leachability (R2 = 0.92 in Korean leachate) of PCDD/DF from contaminant sources. Despite this high linearity between dissolved organic carbon and dissolved PCDD/DF, we observed no strong relationship between dissolved organic carbon and solid phase PCDD/DF (R2 = 0.001). Dissolved organic carbon scarcely affects dissolved PCDD/DF to be combined with solids. As a result, it is not appropriate for incinerated ash to be dumped with municipal solid wastes, as they have a large potential to result in high levels of organic matter, and therefore PCDD/DF, in leachate.     

Testing of a sampling system and analytical method for determination of semivolatile organic compounds in ambient air

A sampling system and analytical procedure for determining PCDD/Fs, PCBs, HCB, and PAHs in ambient air was tested. The reproducibility of the concentrations and the gas/particle partitioning was ± 10% for most compounds. The removal of gaseous compounds on the XAD resin trap was greater than 99%. The adsorption of gaseous substances on the glass fiber filter was negligible for compounds primarily found in the gas phase, but could not be ruled out for compounds found mainly on particles.     

Reduction of dioxin emission by a multi-layer reactor with bead-shaped activated carbon in simulated gas stream and real flue gas of a sinter plant

A laboratory-scale multi-layer system was developed for the adsorption of PCDD/Fs from gas streams at various operating conditions, including gas flow rate, operating temperature and water vapor content. Excellent PCDD/F removal efficiency (>99.99%) was achieved with the multi-layer design with bead-shaped activated carbons (BACs). The PCDD/F removal efficiency achieved with the first layer adsorption bed decreased as the gas flow rate was increased due to the decrease of the gas retention time. The PCDD/F concentrations measured at the outlet of the third layer adsorption bed were all lower than 0.1 ng I-TEQ Nm⁻³. The PCDD/Fs desorbed from BAC were mainly lowly chlorinated congeners and the PCDD/F outlet concentrations increased as the operating temperature was increased. In addition, the results of pilot-scale experiment (real flue gases of an iron ore sintering plant) indicated that as the gas flow rate was controlled at 15 slpm, the removal efficiencies of PCDD/F congeners achieved with the multi-layer reactor with BAC were better than that in higher gas flow rate condition (20 slpm). Overall, the lab-scale and pilot-scale experiments indicated that PCDD/F removal achieved by multi-layer reactor with BAC strongly depended on the flow rate of the gas stream to be treated.     

A design of two simple models to predict PCDD/F concentrations in vegetation and soils

The vegetation and soil levels of the 17 polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) toxic congeners were calculated by means of a vegetation and a soil model, respectively. Both models predicted the levels of the 17 PCDD/F congeners in quite good agreement with the observed results although the soil model was more accurate than the vegetation model. Four different pathways of contribution to the vegetation concentrations were taken into account: vapour-phase absorption, dry particle deposition, wet particle deposition and uptake by root. The most important pathway was the vapour-phase absorption and the less was the uptake by root. In the soils model four pathways were considered: background soil concentration, dry particle deposition, wet particle deposition and uptake by root. After the background concentration, the most important pathway was the wet deposition.     

Effect of pH and temperature on the kinetics of odor oxidation using chlorine dioxide

Increasing public concerns over odors and air regulations in nonattainment zones necessitate the remediation of a wide range of volatile organic compounds (VOCs) generated in the poultry-rendering industry. Currently, wet scrubbers using oxidizing chemicals such as chlorine dioxide (ClO2) are utilized to treat VOCs. However, little information is available on the kinetics of ClO2 reaction with rendering air pollutants, limiting wet scrubber design and optimization. Kinetic analysis indicated that ClO2 does not react with hexanal and 2-methylbutanal regardless of pH and temperature and implied that aldehyde removal occurs primarily via mass transfer. Contrary to the aldehydes, ethanethiol or ethyl mercaptan (a model compound for methanethiol or methyl mercaptan) and dimethyl disulfide (DMDS) rapidly reacted with ClO2. The overall reaction was found to be second and third order for ethanethiol and DMDS, respectively. Moreover, an increase in pH from 3.6 to 5.1 exponentially increased the reaction rate of ethanethiol (e.g., k2 = 25-4200 L/mol/sec from pH 3.6 to 5.1) and significantly increased the reaction rate of DMDS if increased to pH 9 (k3 = 1.4 x 10(6) L2/mol2/sec). Thus, a small increase in pH could significantly improve wet scrubber operations for removal of odor-causing compounds. However, an increase in pH did not improve aldehyde removal. The results explain why aldehyde removal efficiencies are much lower than methanethiol and DMDS in wet scrubbers using ClO2.     

Information Required for the Selection and Performance Evaluation of Wet Scrubbers

The term “wet scrubber” or simply “scrubber,” for the purpose of this report, is intended to include any device using liquid to effect the removal of solid or liquid particles which are entrained in process air or gas streams. This guide is intended to provide information required for the selection and performance evaluation of all types of scrubbers installed for the primary purpose of removing such particulates from any process gas stream. It is not intended to cover scrubbers for the collection of gaseous and/or vapor constituents which involve gas absorption mechanisms.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in plywood combustion gas

Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/DF) levels in plywood combustion gas were investigated for the effects of ammonium chloride (NH4Cl) and paint. For combustion systems in which neither NH4Cl nor paint were present in the plywood samples, total amounts of PCDD/DFs in the combustion gas were in the order of 35-529 ng/Nm3, and were higher in the systems with softwood trees than broadleaf ones, depending on the Cl concentrations. For the systems with added NH4Cl and no paint, and those without NH4Cl but were painted, higher PCDD/ DF rates were observed at combustion temperatures of 270 degrees C and 500 degrees C, respectively. However, for the systems with both NH4Cl and paint, their amounts in the range of 0.6-13 ng/Nm3 were the lowest in all systems. The PCDD/DF abundance profiles were similar to their patterns in pentachlorophenol (PCP). Furthermore, it was found that the 2,3,7,8-chlorine substituted penta- and hexa-CDDs contributed more than other 2,3,7,8-chlorine substitutes to toxicity equivalency (TEQ).     

Partition and size distribution of heavy metals in the flue gas from municipal solid waste incinerators in Taiwan

This study investigates the partition of heavy metals in both solid and gas phases in the flue gas from municipal solid waste (MSW) incinerators. Six MSW incinerators in Taiwan were examined and heavy metals in the flue gas at the inlets and outlets of air pollution control devices (APCDs) were analyzed. Heavy metals including Hg, Pb, Cd, Zn, Cu and Cr were sampled by USEPA Method 29 and further analyzed using inductively coupled plasma-mass spectroscopy (ICP-MS) and cold vapor atomic absorption spectrometry (CVAAS). Experimental results revealed that the removal efficiencies of the APCDs for the heavy metals Pb, Cd, Zn, Cu and Cr greatly exceeded 90%, but that of Hg did not. Two groups of heavy metals upstream of APCDs were observed. Pb, Cd, Zn, Cu and Cr were present mainly in the solid phase with a solid to gas ratio (S/G) of over 12.3. However, in most cases, mercury appeared mainly in the gas phase with an S/G ratio from 0.15 to 1.04, because it has a low boiling point. Additionally, treatment with the APCDs increased the S/G ratio of mercury because gaseous mercury could be removed by injecting powdered activated carbon (PAC) into the flue gas. Moreover, the distribution of particle sizes in the solid phase was bimodal. Finer particles (d(p)2.5 microm) contained more Cr and Hg.     

Atmospheric particle size distributions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) and their implications for wet and dry deposition

Concurrent measurements of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) in different size fractions of atmospheric particulate matter are presented for a winter and a summer sampling period. The PCDD/Fs and PAHs were primarily associated with particles of <1.35 μm aerodynamic diameter. The particle size distributions were similar for the compounds within each substance group and, surprisingly, also between the PCDD/Fs and PAHs. Changes in the particle size distribution of particle mass were reflected in the particle size distributions of the PCDD/Fs and PAHs.The data were employed to identify those particle size fractions dominating the wet and dry particle bound deposition of PCDD/Fs and PAHs and, furthermore, to assess the relative contributions of wet and dry deposition to the total particle bound deposition fluxes. The calculations indicate that coarse particles contribute most to the dry deposition while, in contrast, the wet deposition of the PCDD/Fs and PAHs is dominated by fine particles. Furthermore, it is estimated that in Bayreuth wet deposition dominates the total particle bound deposition of PCDD/Fs and PAHs.     

Dioxins and furans in emissions from medical waste incinerators

Dioxins and furans were detected in emissions from eight medical waste incinerators tested in California. Total uncontrolled emissions ranged from 363 to 11, 811 nanograms per dry standard cubic meter. The most effective of three wet scrubbers achieved an emissions control efficiency of 95 percent for total PCDD and PCDF. A baghouse was less than 30 percent efficient in removing PCDD and PCDF from the incinerator emissions.     

Catalytic oxidation of gaseous PCDD/Fs with ozone over iron oxide catalysts

Catalytic oxidation of PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) with ozone (catalytic ozonation) over nano-sized iron oxides (denoted as FexOy) was carried out at temperature of 120-180 degrees C. The effects of operating temperature, ozone concentration, space velocity (SV) and water vapor contents on PCDD/F removal and destruction efficiencies via catalytic ozonation were investigated. High activity of the iron oxide catalyst towards PCDD/F decomposition was observed even at low temperatures with the aid of ozone. The PCDD/F removal and destruction efficiencies achieved with FexOy/O3 at 180 degrees C reach 94% and 91%, respectively. In the absence of ozone, the destruction efficiencies of all PCDD/F congeners are below 20% and decrease with increasing chlorination level of PCDD/F congener at lower temperature (120 degrees C). However, in the presence of ozone, the destruction efficiencies of all PCDD/F congeners are over 80% on FexOy/O3 at 180 degrees C. Higher temperature and ozone addition increase the activity of iron oxide for the decomposition of PCDD/Fs. Additionally, in the presence of 5% water vapor, the destruction efficiency of the PCDD/Fs is above 90% even at lower operating temperature (150 degrees C). It indicates that the presence of appropriate amount of water vapor enhances the catalytic activity for the decomposition of gas-phase PCDD/Fs.     

Characterization of polychlorinated dibenzo-p-dioxins and dibenzofurans in different particle size fractions of marine sediments

The distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) was examined according to particle size in marine sediments, with a particular focus on fine particulates. Samples from different coastal sites were fractionated into five size groups (<2, 2-5, 5-10, 10-20, and 20-63 microm diameter) by gravitational split-flow thin fractionation. Despite the different size profiles and PCDD/F contents of the sediments at each site, PCDD/F levels in fractionations tended to increase as the particle size decreased; the PCDD/F levels in the finest particles were up to 16 times higher than in the coarsest particles, which was associated with their organic carbon contents. Log normalization showed high levels of PCDD/Fs in the fine silt particles (2-10 microm), which are consumable by aquatic biota. Because of the different toxicity and bioavailability of PCDD/Fs in different sediment particle sizes, it is important to study particle actions to understand their effects on the aquatic ecosystem.     

Mesoscale behavior study of collector aggregations in a wet dust scrubber

In order to address the bottleneck problem of low fine-particle removal efficiency of self-excited dust scrubbers, this paper is focused on the influence of the intermittent gas-liquid two-phase flow on the mesoscale behavior of collector aggregations. The latter is investigated by the application of high-speed dynamic image technology to the self-excited dust scrubber experimental setup. The real-time-scale monitoring of the dust removal process is provided to clarify its operating mechanism at the mesoscale level. The results obtained show that particulate capturing in self-excited dust scrubber is provided by liquid droplets, liquid films/curtains, bubbles, and their aggregations. Complex spatial and temporal structures are intrinsic to each kind of collector morphology, and these are considered as the major factors controlling the dust removal mechanism of self-excited dust scrubbers. For the specific parameters of gas-liquid two-phase flow under study, the evolution patterns of particular collectors reflect the intrinsic, intermittent, and complex characteristics of the temporal structure. The intermittent initiation of the collector and the air hole formation-collapse cyclic processes provide time and space for the fine dust to escape from being trapped by the collectors. The above mesoscale experimental data provide more insight into the factors reducing the dust removal efficiency of self-excited dust scrubbers.

Implications: This paper focuses on the reconsideration of the capturer aggregations of self-excited dust scrubbers from the mesoscale. Complex structures in time and space scales exist in each kind of capturer morphology. With changes of operating parameters, the morphology and spatial distributions of capturers diversely change. The change of the capturer over time presents remarkable, intermittent, and complex characteristics of the temporal structure.     

Validation of modeling approach to evaluate congener-specific concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans in air and soil near a solid waste incinerator.

A concise modeling approach using long-term averaged meteorological data was developed to estimate site-specific concentrations of congeners of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) near a solid waste incinerator. This approach consists of calculation of atmospheric dispersion, dry and wet deposition of gaseous and particle-bound congeners, and non-steady-state concentrations in soil. The predictability of this approach was evaluated by comparison of calculated concentrations of congeners in soil with those measured at eight locations near a municipal solid waste incinerator (MSWI). The variation of these concentrations due to variability of meteorological parameters is small. A considerable number of mean values show good agreement with measured concentrations within a factor of three. The reasonable agreement between calculated and measured concentrations indicates that algorithms for the calculation of vapor-phase deposition and non-steady-state concentrations in soil must be included in the modeling approach for an accurate estimation of the concentrations of congeners of PCDD/Fs emitted from MSWIs to the atmosphere. For a detailed estimation of site-specific concentrations, it is important to specify the bulk density of soil in the evaluated area, together with meteorological parameters.