PAH emissions from coal combustion and waste incineration.

The characteristics of PAHs that are emitted by a municipal waste incinerator (MWI) and coal-fired power plant are examined via intensive sampling. Results of flue gas sampling reveal the potential for PAH formation within the selective catalytic reduction (SCR) system of a coal-fired power plant. In the large-scale MWI, the removal efficiency of PAHs achieved with the pilot-scaled catalytic filter (CF) exceeds that achieved by activated carbon injection with a bag filter (ACI+BF) owing to the effective destruction of gas-phase contaminants by a catalyst. A significantly lower PAH concentration (1640ng/g) was measured in fly ash from a CF module than from an ACI+BF system (5650ng/g). Replacing the ACI+BF system with CF technology would significantly reduce the discharge factor (including emission and fly ash) of PAHs from 251.6 to 77.8mg/ton-waste. The emission factors of PAHs that are obtained using ACI+BF and the CF system in the MWI are 8.05 and 7.13mg/ton, respectively. However, the emission factor of MWI is significantly higher than that of coal-fired power plant (1.56mg/ton). From the perspective of total environmental management to reduce PAH emissions, replacing the original ACI+BF process with a CF system is expected to reduce environmental impact thereof.

Simultaneous removal of PCDD/Fs, pentachlorophenol and mercury from contaminated soil.

Pentachlorophenol (PCP), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and mercury were simultaneously removed from heavily contaminated soil using a continuous pilot-scale thermal system (CPTS). Operating the system at 700 °C with 22 min of retention time ensured that the residual contaminants in remediated soil are lower in concentration than the soil standards of Taiwan EPA require. Both PCP and PCDD/Fs are effectively destroyed during the treatment at high temperatures in the CPTS, but significant dechlorination of PCDD/Fs is also found, resulting in lower net destruction efficiencies of TCDD/F and PeCDD/F-congeners, compared with those of highly chlorinated Hx-, Hp- and OCDD/F congeners. Moreover, 2,3,7,8-TetraCDD is significantly formed if the retention time is not long enough for total destruction. Inadequate reaction time (or retention time) even may lead to a rise in TEQ-value due to incomplete dechlorination. Mercury is significantly desorbed from contaminated soil and discharged through the exhaust. For PCP and PCDD/Fs, the exhaust discharge percentages including both the remediated soil and the exhaust are <0.03% and 1.14% of the input, respectively, achieved with 700 °C and 33 min retention time. In contrast, some 97.8% of input mercury rate is desorbed and discharged via the exhaust, so that the latter should be carefully cleaned via efficient air pollution control devices, whereas this contribution focuses on the conditions required for reaching adequate soil cleaning.

Continuous sampling of MSWI dioxins.

Municipal solid waste incineration (MSWI) is generally considered as a well-controlled source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), in brief dioxins. Start-up conditions continue, however, to be problematic. A self-developed continuous sampler was specially designed and built to fulfill the various sampling criteria of U.S. EPA Method 23 and monitor the trends of dioxins emissions during diverse operating conditions. In the MSWI plant investigated, a 98.1% TEQ PCDD/F removal efficiency was achieved in normal operation using activated carbon injection + bag filtration (ACI + BF) and the corresponding PCDD/F emission remains well below the standard set by Taiwan EPA (0.1 ng I-TEQ/Nm(3) @ 11% O2). During start-up, however, continuous sampling indicates that this limit value is reached only after 12 and 9 days, respectively for the 1st (2011) and 2nd test campaign (2012). Only 15 days after start-up the PCDD/F emissions shrunk to the levels typically measured during normal operation. The PCDD/F emissions from the 1st and 2nd continuous sampling campaigns were 5.4 and 5.5 mg I-TEQ, respectively. Short-term PCDD/F sampling such as the U.S. EPA Method 23 is less adapted to monitor these transient PCDD/F emissions representatively and accurately, due to a steady decrease of PCDD/F emissions after start-up. This self-developed continuous sampler effectively enhances the ease and reliability of emission data collecting during transient conditions of MSWI.

Catalytic destruction vs. adsorption in controlling dioxin emission.

This study investigates the removal efficiencies of PCDD/Fs achieved with a catalytic filter (CF) and with activated carbon injection followed by bag filter (ACI+BF) as applied in an industrial waste incinerator (IWI) and a hazardous waste incinerator (HWI), respectively. Catalytic filtration has been successfully applied to remove PCDD/Fs from gas streams. Comparing the CF to the ACI+BF system, it appears that the PCDD/F removal efficiency achieved with a CF is higher than that of an ACI+BF system. The PCDD/F emissions from both incinerators are well controlled to meet the regulatory limit of 0.1 ng I-TEQ/Nm(3). Additionally, the PCDD/F concentration in BF ash is higher than the regulation limit of Taiwan (1.0 ng I-TEQ/g). In contrast, the PCDD/F concentration in CF ash is only 0.274 ng I-TEQ/g. The difference is attributed to the fact that the ACI+BF system just transfers PCDD/Fs from gas phase to solid phase and further increases the PCDD/F concentration in fly ash, while CF technology effectively destroys the gas-phase PCDD/Fs. Therefore, the disposal of the fly ash discharged from CF would be less expensive compared with the fly ash discharged from the ACI+BF system. In this study, the PCDD/F emission factors of both incinerators are also established.

Characteristics of PCDD/F emissions from secondary copper smelting industry.

Characteristics and mechanisms of PCDD/F formation with different feed materials in secondary copper smelting industry are investigated. The results indicate that PCDD/Fs are significantly formed even with the reaction time less than 0.1s, especially when the material containing high residues (Cu3) is fed. High copper content (65±2%) in the feed material enhances PCDD/F formation rate. Memory effect and de novo synthesis are two important mechanisms leading to PCDD/F formation. PCDD/F concentrations at the cyclone's inlet are between 2.92 and 12.4ng-TEQNm(-3) and increase with increasing residue content in the feed material. Two regions are identified for high potential of PCDD/F formation including the brass melt surface of the induction furnace and piping before the induced draft fan of the inlet hood. PCDD/Fs in flue gas are effectively removed with a cyclone and bag filter at low operating temperatures (<60°C) to meet the emission limit of 1.0ng-TEQNm(-3). 1,2,3,4,6,7,8-HpCDF has the largest mass fraction of PCDD/Fs and can serve as a fingerprint for emissions from secondary copper smelting processes. The total emission factor of PCDD/Fs from flue gas, residual and fly ash in the secondary copper smelting process investigated is 22.01µg-TEQtonne(-1).

Pilot tests on the catalytic filtration of dioxins.

Tests were conducted to study the removal efficiencies (REs) of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from flue gas during a test program involving a pilot-scale catalytic filter (CF) module and a full-scale municipal solid waste incinerator (MSWI). The REs attained with the CF on a side stream and a conventional activated carbon (AC) injection and baghouse filtration system in the full-scale MSWI are evaluated via simultaneous sampling and analysis of both gas- and particle-phase PCDD/Fs. Flue gas without AC is supplied to the pilot-scale CF module for evaluating its RE capabilities. The REs achieved with the CF at 180 °C are 96.80 and 99.50%, respectively, for the gas phase and the particulate contained. The gas-phase PCDD/F RE rises significantly at 200 and 220 °C. The air/cloth (A/C) ratio defined as is the gas flow rate (m(3)/min) divided by the filtration area (m(2)) also affects the PCDD/F RE, especially in the gas phase. At 180 °C, a RE of gas-phase PCDD/Fs of 95.94% is attained with the CF at 0.8 m/min, yet it decreases at higher A/C ratios (1 and 1.2 m/min). A significantly lower toxic equivalency (TEQ) concentration (0.71 ng I-TEQ/g) was measured in the filter dust of the CF module compared to that collected by the AC adsorption system (4.18 ng I-TEQ/g), apparently because of the destruction of gas-phase PCDD/Fs by the catalyst.

Pyrolysis of MWI fly ash -- effect on dioxin-like congeners.

Removal and destruction of dioxin-like congeners, including polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs), from fly ash were investigated at varying pyrolysis temperatures and reaction times and using calcium-based additives. Destruction efficiencies based on TEQ and mass both increase with rising treatment temperature. However, additional low chlorinated PCDD/Fs were formed significantly by dechlorination of high chlorinated PCDD/Fs, at pyrolysis temperatures of 250 and 300°C. Surprisingly, lower destruction efficiencies were realized in the presence of Ca-based additive, compared with those without additive, and TEQ values of fly ash into which CaO was introduced increased, compared with the raw ash, due to significant formation of low chlorinated PCDD/Fs (4-5 Cl). However, complex interactions among unburned carbon, sulfur and metals in the fly ash collected in this study make it difficult to pinpoint the exact causes. The results obtained in this study indicate that degradation and formation of dioxin-like congeners take place simultaneously in pyrolysis process, such as formation of low chlorinated PCDD/Fs via dechlorination of highly chlorinated PCDD/Fs.

Characteristics of dioxin emissions from a Waelz plant with acid and basic kiln mode.

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were measured in the flue gas of a Waelz plant operated in acid and basic modes, respectively. To abate (PCDD/F) and other pollutants, the plant operates with a post-treatment of flue gases by activated carbon injection and subsequent filtration. Relatively high PCDD/F discharge by fly ashes is found with acid kiln mode of the Waelz process. Therefore, basic kiln mode of the Waelz process is investigated and compared in this plant. With the adsorbent injection rate of 7 kg/h (95 mg/Nm(3)), the PCDD/F concentration in stack gas was measured as 0.123 ng I-TEQ/Nm(3) in the basic operating mode. The added Ca(OH)(2) reacted with metal catalysts and HCl((g)) in the flue gas and thus effectively suppressed the formation of PCDD/Fs. PCDD/F concentrations in fly ashes sampled from the dust settling chamber, cyclone, primary filter and secondary filter in basic kiln mode were significantly lower than that in acid kiln mode. Total PCDD/F emission on the basis of treating one kg of electric arc furnace dust in the basic operation mode was 269 ng I-TEQ/kg EAF-dust treated which was significantly lower than that in acid mode (640 ng I-TEQ/kg EAF-dust treated).

Evaluation of PCDD/F oxidation catalysts: confronting studies on model molecules with tests on PCDD/F-containing gas stream.

Titania supported vanadium oxide is a renowned catalyst for the abatement of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) from gas effluents. To develop more active formulations, researchers mainly rely on lab-scale experiments on "PCDD/Fs-mimicking substances", like (chloro)-benzene. Using such model compounds is convenient whereas handling PCDD/Fs in the laboratory is potentially hazardous and complicated. Recent studies, however, challenged some foremost conclusions of model compound based studies, starting from the observation that different model compounds gave contrasted results. Thus the present work aims at confronting some of these dubious conclusions with direct experimental tests on PCDD/Fs. One reference V(2)O(5)/TiO(2) catalyst and three modified formulations (V(2)O(5)/TiO(2)-SO(4), V(2)O(5)-MoO(3)/TiO(2), and V(2)O(5)-WO(3)/TiO(2)) have been evaluated. A dedicated apparatus was used which allows safe and reliable tests on a mixture of PCDD/Fs congeners. Some of the previously proposed catalyst improvement strategies actually prove to be disadvantageous in the removal of PCDD/Fs. In particular, MoO(3)- and WO(3)-modified catalysts were significantly less active than the reference catalyst. These observations show that conclusions from model compound based studies must be drawn with care and should ideally be confronted with tests on the actual target pollutants.

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.

Degradation of gaseous dioxin-like compounds with dielectric barrier discharges.

Developing effective technologies to reduce dioxin emissions has become an important issue in the research and industrial fields. In this study, a dioxin-containing gas stream generating system was applied to evaluate the effectiveness of dielectric barrier discharge (DBD) plasma technology for the destruction of dioxin-like compounds. The results indicate that the destruction efficiencies of dioxin-like compounds achieved with DBD plasma strongly depend on the composition of the simulated gas stream. As the DBD plasma is operated with the simulated gas stream containing 20% water vapor, around 74% PCDDs and 89% PCDFs can be destroyed by DBD plasma. UV, electrons, and OH radicals are generated via the DBD plasma process and react with the dioxin-like compounds in the gas stream. Dechlorination via UV and electrons and decomposition via OH radicals occur at the same time and significantly increase the destruction efficiency of PCDD/Fs in the presence of oxygen and water vapor. Additionally, the total toxicity destruction of dioxin-like compounds with the input energy of 1 kJ increases from 1.47 to 3.06 ng-TEQ(WHO) as the water vapor is incorporated into the gas stream.