Ming-Xiu Zhan

Inhibition of the de novo synthesis of PCDD/Fs on model fly ash by sludge drying gases

Sludge drying gases (SDG), evolving from drying and mild thermal decomposition (<300°C) of raw sewage sludge contain NH3 and SO2 as well as other N- and S-compounds. All of these are potential PCDD/Fs suppressants. It is indeed observed that these SDG suppress 2,3,7,8-substitued PCDD/Fs formation on Model Fly Ash (MFA) with an efficiency up to 97.6% in wt. units and 96% in I-TEQ, respectively. This suppression is strong for (the bulk of) PCDD/Fs, adsorbed on the model fly ash; conversely, sludge drying gases enhance PCDD/Fs desorption from MFA. Moreover, TCDD/Fs are suppressed least, possibly following stepwise dechlorination of higher chlorinated PCDD/Fs. Characteristics, such as the type, origins and amount of sludge, its moisture-, nitrogen- and sulfur content and the nature of the thermal treatment applied are all expected to influence upon the suppression capabilities. In this study three types of dry sludge are tested and applied as suppressant in four different amounts or modes. The quality of the sludge drying gases is continuously monitored: the Gasmet results reveal that NH3 and SO2 are the most important components of SDG. The MFA reaction residue is scrutinized by Scanning Electron Microscope (SEM) and Energy Dispersive Spectrometer (EDS) analysis. A large number of particles attaching to the surface of model fly ash are observed by SEM. Moreover, EDS analysis reveals that part of the chlorine in MFA is carried away with the SDG and replaced by sulfur, so that eliminating chlorine may be part of the inhibition mechanism. However, further research is still needed to establish the optimum operating modes and to confirm the role of both inorganic and organic nitrogen and sulfur compounds in the suppression of PCDD/Fs formation on model fly ash.

Simultaneous suppression of PCDD/F and NOx during municipal solid waste incineration

Thiourea was tested as a dioxins inhibitor in a full-scale municipal solid waste incinerator with high capacity (34 t h(-1)). The suppressant, featuring a high S- and N-content, was converted into liquor and then injected (35 kg h(-1)) into the furnace (850 °C) through the inlets already used for Selective Non-Catalytic Reduction (SNCR) of flue gas NOx. The first results show that thiourea reduces the dioxins in flue gas by 55.8 wt.%, those in fly ash by 90.3 wt.% and the total dioxins emission factor by 91.0 wt.%. The concentration of PCDD/Fs was 0.08 ng TEQ Nm(-3), below the national standard of 0.1 ng TEQ Nm(-3). The weight average chlorination degree of dioxins decreases slightly after adding the inhibitor, indicating that it suppresses both the formation and the chlorination of dioxins. Analysis of fly ash by scanning electron microscope (SEM) suggests that the particle size becomes larger after adding the inhibitor. Further analysis using an energy dispersive spectrometer (EDS) reveals that the sulphur content in fly ash rises, but the chlorine content declines when adding thiourea. These results suggest that poisoning the metal catalyst and blocking the chlorination are probably responsible for suppression. NOx reduction attains 42.6 wt.%. These tests are paving the way for further industrial application and assist in controlling the future emissions of dioxins and NOx from MSWI.

Suppression of dioxins after the post-combustion zone of MSWIs

Thiourea was selected as representative of combined S- and N-inhibitors and injected after the post-combustion zone of two full-scale municipal solid waste incinerators (MSWIs) using a dedicated feeder. Firstly, the operating conditions were scrutinised by monitoring the concentrations of SO2, NH3 and HCl in the clean flue gas. The suppression experiment showed that in MSWI A thiourea could reduce the total I-TEQ value in flue gas by 73.4% from 1.41ng I-TEQ/Nm(3) to 0.37I-TEQ/Nm(3), those in fly ash by 87.1% from 14.3ng I-TEQ/g to 1.84I-TEQ/g and the total dioxins emission factor by 87.0wt.%, with a (S+N)/Cl molar ratio of 9.4. The suppression efficiencies of PCDD/Fs in flue gas and fly ash in MSWI B could be up to 69.2% and 83.0% when the (S+N)/Cl molar ratio attained 7.51. Furthermore, the congener distributions of dioxins were also analysed in the flue gas and fly ash, before and after addition of thiourea, to find cues to some suppression mechanism. In addition, the filtered fly ash was explored by the Scanning Electron Microscope (SEM) and Energy Dispersive Spectrometer (EDS) analysis of fly ash. These results suggest that poisoning the metal catalyst and blocking the chlorination are most probably responsible for suppression.

Dioxins from medical waste incineration: Normal operation and transient conditions:

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are key pollutants in waste incineration. At present, incinerator managers and official supervisors focus only on emissions evolving during steady-state operation. Yet, these emissions may considerably be raised during periods of poor combustion, plant shutdown, and especially when starting-up from cold. Until now there were no data on transient emissions from medical (or hospital) waste incineration (MWI). However, MWI is reputed to engender higher emissions than those from municipal solid waste incineration (MSWI). The emission levels in this study recorded for shutdown and start-up, however, were significantly higher: 483 ± 184 ng Nm-3 (1.47 ± 0.17 ng I-TEQ Nm-3) for shutdown and 735 ng Nm-3 (7.73 ng I-TEQ Nm-3) for start-up conditions, respectively. Thus, the average (I-TEQ) concentration during shutdown is 2.6 (3.8) times higher than the average concentration during normal operation, and the average (I-TEQ) concentration during start-up is 4.0 (almost 20) times higher. So monitoring should cover the entire incineration cycle, including start-up, operation and shutdown, rather than optimised operation only. This suggestion is important for medical waste incinerators, as these facilities frequently start up and shut down, because of their small size, or of lacking waste supply. Forthcoming operation should shift towards much longer operating cycles, i.e., a single weekly start-up and shutdown.

Suppression of dioxins in waste incinerator emissions by recirculating SO2.

Sulphur is an effective inhibitor of the formation of Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzo-furans (PCDD/Fs), as was proven in laboratory and pilot plant studies. In this study, a pilot-scale system with capacity 300 N m(3) h(-1) was situated at the bypass of an actual hazardous waste incinerator (HWI) and tested to reduce the emission of PCDD/Fs. Activated carbon was used as a medium to adsorb SO2 from flue gas and release it again at the higher temperature of filtered ash detoxification to achieve SO2 circulation in the system. Most PCDD/Fs in the filtered ash are decomposed by thermal treatment. Experimental results indicate that the system is capable of stable operation with SO2 accumulation at a high level of concentration and a high reduction efficiency of PCDD/Fs. A reduction of more than 80% was already achieved without addition of other sulphur compounds. When pyrite (FeS2) was added the reduction of PCDD/Fs could reach 94%, with a residual PCDD/Fs concentration in the flue gas as low as 0.13 ng TEQ N m(-3). This SO2 recirculating and suppression technology potentially provides significant progress for dioxin emission control in waste incineration and could be useful for controlling emissions of PCDD/Fs and other chlorinated organic chemicals in China.

Emission characteristics and relationships among PCDD/Fs, chlorobenzenes, chlorophenols and PAHs in the stack gas from two municipal solid waste incinerators in China

An extensive investigation was conducted to understand polychlorinated dibenzo-p-dioxin and furan (PCDD/F) formation mechanisms and their relationships with chlorobenzenes (CBzs), chlorophenols (CPhs) and polycyclic aromatic hydrocarbons (PAHs) in the stack gas from two fluidized bed municipal solid waste incinerators in China. The toxic equivalent quantity (TEQ) value and the concentration of target compounds changed with the incinerator operating conditions. CPhs and PAHs were much more sensitive to operation conditions and were affected more easily by change. Only 2-monochlorophenol revealed a negative linear correlation (R2 ≥ 0.7). More than half of the PAHs revealed an adequate correlation model with PCDD/F concentration (R2 > 0.6), while CBzs showed almost perfect correlations with PCDD/Fs (R2 ≥ 0.8, significance level α ≤ 0.05). 123-Trichlorobenzene, 1234-tetrachlorobenzene and pentachlorobenzene revealed the best positive linear correlation (R2 > 0.9). PCDFs were revealed to be the best target compounds for indication due to the similar formation variation trend to that of other precursors. Unary and multiple linear regression equations with high coefficients of determination between several CBz, PAHs and PCDD/Fs, TEQ and PCDFs were established. The detailed relationships among PCDD/F homologues, isomers and other compounds and their formation mechanism were also discussed.

High temperature suppression of dioxins.

Combined Sulphur-Nitrogen inhibitors, such as sewage sludge decomposition gases (SDG), thiourea and amidosulphonic acid have been observed to suppress the de novo synthesis of dioxins effectively. In this study, the inhibition of PCDD/Fs formation from model fly ash was investigated at unusually high temperatures (650 °C and 850 °C), well above the usual range of de novo tests (250-400 °C). At 650 °C it was found that SDG evolving from dried sewage sludge could suppress the formation of 2,3,7,8-substituted PCDD/Fs with high efficiency (90%), both in weight units and in I-TEQ units. Additionally, at 850 °C, three kinds of sulphur-amine or sulphur-ammonium compounds were tested to inhibit dioxins formation during laboratory-scale tests, simulating municipal solid waste incineration. The suppression efficiencies of PCDD/Fs formed through homogeneous gas phase reactions were all above 85% when 3 wt. % of thiourea (98.7%), aminosulphonic acid (96.0%) or ammonium thiosulphate (87.3%) was added. Differences in the ratio of PCDFs/PCDDs, in weight average chlorination level and in the congener distribution of the 17 toxic PCDD/Fs indicated that the three inhibitors tested followed distinct suppression pathways, possibly in relation to their different functional groups of nitrogen. Furthermore, thiourea reduced the (weight) average chlorinated level. In addition, the thermal decomposition of TUA was studied by means of thermogravimetry-fourier transform infrared spectroscopy (TG-FTIR) and the presence of SO2, SO3, NH3 and nitriles (N≡C bonds) was shown in the decomposition gases; these gaseous inhibitors might be the primary dioxins suppressants.

Comparative analyses of catalytic degradation of PCDD/Fs in the laboratory vs. industrial conditions

This study investigates the efficiencies and mechanisms of the catalytic degradation of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) first, in simulated laboratory conditions and then, in a commercial municipal solid waste incineration (MSWI) plant. Five commercially available V2O5-WO3/TiO2 (VWTi) catalysts were tested. The degradation efficiency of PCDD/Fs in the simulated flue gas ranged 22.8-91.7% and was generally higher than that in the MSWI flue gas of 8.0-85.4%. The degradation efficiency of PCDD/Fs in the real flue gas of the MSWI plant was largely hindered by the complex composition of the flue gas, which could not be completely reproduced in the simulated laboratory conditions. Furthermore, the degradation of the higher chlorinated PCDD/Fs was easier compared to the lower chlorinated ones in the presence of the VWTi catalysts, which was primarily driven by the tendency of the higher chlorinated PCDD/Fs to be adsorbed on the surface of the catalyst and further destructed due to their lower vapor pressure. In addition, powdered catalysts should be preferred over the honeycomb shaped ones as they exposed higher PCDD/Fs degradation efficiencies under equal reaction conditions. The chemical composition and a range of the relevant to the study properties of the catalysts, such as surface area, crystallinity, oxidation ability, and surface acidity, were analyzed. The study ultimately supports the identification of the preferred characteristics of the VWTi catalysts for the most efficient degradation of toxic PCDD/Fs and elucidates the corresponding deactivation reasons of the catalysts.