Modification of activated carbon using urea to enhance the adsorption of dioxins.

Activated carbon is commonly used to remove dioxins from flue gas via adsorption. Improving the targeted adsorption capacity of activated carbon for dioxins can reduce the consumption of adsorbents and help achieve emission standards for target pollutants. Here, commercial coal-based activated carbon was used as a raw material and modified by urea impregnation along with treatment at high temperature under a nitrogen atmosphere. It was found that modification with urea effectively improved the pore structure of activated carbon while incorporating a certain amount of nitrogen. The best modification effect was achieved at a modification temperature of 600 °C, an impregnation ratio of urea to activated carbon of 1:1, and with high-temperature treatment for 2 h. The mesopore volume of the modified activated carbon (AC600) reached 0.38 cm3/g, accounting for 57.58% of the total pore volume. With an impregnation ratio of urea to activated carbon of 1:1, high-temperature treatment for 2 h, and a modification temperature of 800 °C, a certain amount of nitrogen was introduced into the carbon rings to form a modified activated carbon (AC800) rich in pyridine and pyrrole groups (atomic percentage = 4.84%). The activated carbon modified by urea and the unmodified activated carbon were subsequently selected for dioxin adsorption experiments using a dioxin generation and adsorption system. AC600 showed the highest adsorption efficiency for dioxins, reaching 97.65%, based on toxicity equivalents. Although AC800 has poor pore properties, it has more pyridine and pyrrole groups than AC600. Consequently, the efficiency of AC800 at adsorbing low-concentration dioxins reached 85.24% based on toxicity equivalents. Overall, this study describes two mechanisms for effectively modifying activated carbon with urea based on (1) optimizing the pore structure of activated carbon and (2) incorporating nitrogen.

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.

Distribution of gasification products and emission of heavy metals and dioxins from municipal solid waste at the low temperature pyrolysis stage.

Gasification is widely regarded as one of the most practical, economical, and environmentally friendly waste disposal technologies for municipal solid waste (MSW). The pyrolysis stage (300-500 °C) is crucial for weight loss during MSW gasification, as a considerable amount of organic matter breaks down, producing high-value synthesis gas. This study investigated the product distribution and pollutant emission characteristics within this temperature range and its influencing factors during MSW gasification using a self-designed MSW gasification device. Results indicated that MSW underwent approximately 70% weight loss within this temperature range, yielding low amounts of inorganic and short-chain organic products, with mainly long-chain organic compounds of C16-C34. The atmosphere variation had minimal effect on the elemental composition and content of solid phase products. X-ray fluorescence spectrometry (XRF) and inductively coupled plasma mass spectrometry (ICP-MS) analyses showed that Mn and Zn were the primary components of heavy metal leaching toxicity in solid phase products, with their contents increasing as temperature increased. Synthesis gas showed the highest content of heavy metal As element, reaching a peak at 400 °C. Higher gasification temperature and lower oxygen flow rate significantly reduced the dioxin content and I-TEQ values, with highly chlorinated isomers being the predominant dioxin isomers. Nonetheless, low-chlorinated dioxins accounted for more than 50% of the I-TEQ. This study improves our understanding of the gasification process of MSW.

Dioxin emission and distribution from cement kiln co-processing of hazardous solid waste.

Cement kiln collaborative disposal technology can not only dispose of hazardous waste but also provide energy for the cement industry. However, the addition of hazardous waste may promote the formation of dioxins in cement kilns. In this study, typical hazardous solid wastes, such as solidified fly ash, electroplating sludge, and industrial residue, were co-processed in a cement kiln with different feeding positions and different feeding amounts. The concentrations of dioxins in the flue gas, clinker, and precalciner furnace slag were investigated. The effect of adding mixed hazardous solid waste on the formation of dioxin was also studied. The results showed that the concentration of dioxin in the flue gas without added hazardous waste was 1.57 ng/m3, and the concentration varied from 1.03 to 6.49 ng/m3 after the addition of hazardous waste. In addition, the concentration of dioxin in the flue gas and solid samples increased substantially when the co-processing ratio doubled. The large amount of Cu in solidified fly ash promoted the formation of dioxins, while the higher S content in the electroplating sludge suppressed the formation of dioxins. Compared with the addition of single hazardous waste, the concentration of dioxin in precalciner furnace slag increases by about 300%. Furthermore, the distributions of isomers in the clinker and precalciner furnace slag were similar. 1,2,3,4,6,7,8-HpCDD and OCDD accounted for a large proportion of the mass concentration, and the contribution rate ranged from 48.7 to 82.0%. Most importantly, correlation analysis showed that the concentration of dioxin was closely related to the copper content, hazardous waste types and additive proportion, with correlation coefficients of 0.79, 0.83, and 0.89, respectively. This study provides a basis for exploring the high environmental benefits of disposing of hazardous solid waste by co-processing in cement kilns.

Co-processing of the MSWI flue gas in a lab-scale coal-fired drop-tube furnace.

Coal-fired power plants are characterized by high combustion temperature and well-equipped air pollution control devices. The trace organic pollutants in the municipal solid waste incineration (MSWI) flue gas would be completely destroyed if the MSWI flue gas was injected into the high temperature area of a coal-fired boiler. In this study, the emission characteristics of common gas pollutants, heavy metals, and dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in both flue gas and bottom ash when the MSWI flue gas was injected into a lab-scale coal-fired drop-tube furnace were investigated. After co-processing, the concentrations of NOx, SO2, CO, and all heavy metals in the flue gas emitted from the coal-fired drop-tube furnace did not change a lot. However, the concentration of HCl in the flue gas from drop-tube furnace increased after coupling the MSWI flue gas. Moreover, the I-TEQ values of the PCDD/Fs in the flue gas and bottom ash after coupling the MSWI flue gas were 0.037 ng I-TEQ/Nm3 and 0.63 ng I-TEQ/g, respectively. The main formation pathways of PCDD/Fs in the flue gas of drop-tube furnace were suggested to be de novo synthesis and precursor synthesis. Furthermore, the effects of oxygen content and temperature on the formation of PCDD/Fs were also studied. The reduction efficiencies of the total amount of PCDD/Fs in the flue gas from the co-processing system were more than 60%, and even reached 90%. Therefore, co-processing of the MSWI flue gas in coal-fired power plants might be an environmentally friendly technology.

Parameters affecting the formation mechanisms of dioxins in the steel manufacture process.

With the implementation of the new national standards in the steel industry, dioxins (polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs)) emission and control have attracted more and more attention in China. The PCDD/Fs levels and signatures of nine steelmaking materials and by-products were experimentally analysed and compared, including five kinds of steelmaking fly ash (sintering fly ash, basic oxygen furnace fly ash, electric arc furnace fly ash and two kinds of blast furnace fly), three kind of steel sludge (continuous casting sludge, hot rolling sludge and cold rolling sludge) and sintering raw material. Dioxin formation from the sintering fly ash was highest of all 9 materials. Furthermore, highly chlorinated PCDD/Fs homologues were abundant in that sample, while the profiles were contrary to those of other materials. More importantly, the entire isomer signatures of all 61 samples were analysed, involving various materials, temperatures, oxygen levels, particle size and inhibitors, with special emphasis on those congeners associated with chlorophenol precursor routes, as well as seventeen 2,3,7,8-substituted PCDD/Fs. Strong correlation was found among seven PCDD-congeners of CP-route. The analysis of the molecular structure of these congeners revealed that 2,4,6/2,3,5-trichlorophenol may act as a precursor to form all those PCDD-congeners by condensation. In addition, the influence of various factors (temperature, oxygen level, particle size, inhibitors addition etc.) on the relative importance of CP-route congeners and 2,3,7,8-substituted congeners was discussed, with the goal of shedding more light on the mechanism of PCDD/Fs-formation.

Thermal reaction characteristics of dioxins on cement kiln dust.

Cement kiln dust is commonly recycled back into the production process. This results in elevated concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the flue gases of cement plants. The present study investigated the effects the reaction temperature, oxygen content, and origin of kiln dust had on the thermal reaction characteristics of PCDD/Fs. The concentration of 2,3,7,8-PCDD/Fs that were desorbed from the kiln dust decreased as the reaction temperature was increased and the higher temperature facilitated the degradation of PCDD/Fs. However, the oxygen content, which ranged from 6-21%, had only a minor impact on the thermal reaction characteristics of PCDD/Fs. Finally, the thermal reaction characteristics of PCDD/Fs were largely affected by the origin of the kiln dust; 1.2 pg I-TEQ g-1 was desorbed from kiln dust originating from a cement plant that co-processed refuse-derived fuel (RDF) and 47.5 pg I-TEQ g-1 was desorbed from kiln dust originating from a cement plant that co-processed hazardous waste. The study also found that PCDD/F formation pathways were dependent on the origin of the kiln dust; precursor synthesis dominated PCDD/F formation on the kiln dust collected from a cement plant that co-processed RDF, while de novo synthesis dominated the formation of PCDD/Fs on the remaining samples of kiln dust.

The impact of hydrochloric acid on the catalytic destruction behavior of 1,2-dichlorbenzene and PCDD/Fs in the presence of VWTi catalysts.

Catalytic oxidation is regarded an effective technique to control the emissions of chlorinated benzenes (CBzs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from waste incinerators. Among the numerous factors affecting the degradation efficiency of CBzs and PCDD/Fs, limited attention has been paid to the impact of hydrochloric acid (HCl) present in the flue gas. This study investigates how HCl affects the catalytic degradation of 1,2-dichlorbenzene (1,2-DCBz) at different reaction times and temperature regimes. The results showed that the removal efficiency of 1,2-DCBz, which was achieved by the V2O5/WO3-TiO2 (VWTi) catalyst, decreased the largest by 10% in the presence of HCl. Furthermore, it was found that the increasing concentration of water vapor hindered the degradation efficiency of 1,2-DCBz. No relationship between the process temperature and the destruction efficiency of PCDD/Fs was observed in the presence of HCl. Potential increasing of the removal efficiency of 1,2-DCBz was confirmed by adding different amount of activated carbon (AC) in the presence of HCl.

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.

Low temperature degradation of polychlorinated dibenzo-p-dioxins and dibenzofurans over a VOx-CeOx/TiO2 catalyst with addition of ozone.

In order to find a catalyst to destroy polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) with high efficiency, a homemade VOx-CeOx/TiO2 catalyst was prepared, and then tested in the flue gas of a waste incinerator at temperatures of 180-240 °C. The results shows the best removal efficiency (93.4%) was attained already at 200 °C, yet degradation efficiency further raised with temperature, until 240 °C. Ozone (500 ppm) was also introduced into the system to increase the activity of catalyst, and removal efficiency of PCDD/Fs increased further to 97.4% and 98.8% at 200 and 240 °C, respectively. In addition, a lab-scale reaction system was installed to study the degradation mechanism of PCDD/Fs. Octa-chlorinated dibenzo-p-dioxin (OCDD) was selected as the study object due to the most stable structure and maximum chlorine atom number. The intermediate products resulting from the conversion of OCDD were monitored using gas chromatography/mass spectrometry and Fourier transform infrared spectroscopy and a possible reaction pathway was proposed. Dechlorination persists until the complete conversion of OCDD. Oxidation decomposes OCDD-molecules mainly into organic substances having one, two or more benzene rings, yet also alkanes, cycloalkanes and heterocompounds of sulphur, nitrogen, and halogens appear. However, more work is still needed to fit those trace products into mechanistic schemes.

[Correlation of Persistent Free Radicals, PCDD/Fs and Metals in Waste Incineration Fly Ash].

Environmentally persistent free radicals (EPFRs) are relatively highly stable and found in the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Recent studies have concentrated on model dioxin formation reactions and there are few studies on actual waste incineration fly ash. In order to study EPFRs and the correlation with dioxins and heavy metals in waste incineration fly ash, the spins of EPFRs, concentration of PCDD/Fs and metals in samples from 6 different waste incinerators were detected. The medical waste incineration fly ash from Tianjin, municipal solid waste incineration fly ash from Jiangxi Province, black carbon and slag from municipal solid waste incinerator in Lanxi, Zhejiang Province, all contained EPFRs. Above all the signal in Tianjin sample was the strongest. Hydroxyl radicals, carbon-center radicals and semiquinone radicals were detected. Compared with other samples, Jiangxi fly ash had the highest toxic equivalent quantity (TEQ) of dioxins, up to 7.229 4 ng · g⁻¹. However, the dioxin concentration in the Tianjin sample containing the strongest EPFR signals was only 0.092 8 ng · g⁻¹. There was perhaps little direct numeric link between EPFRs and PCDD/Fs. But the spins of EPFRs in samples presented an increasing trend as the metal contents increased, especially with Al, Fe, Zn. The signal strength of radicals was purposed to be related to the metal contents. The concentration of Zn (0.813 7% ) in the Tianjin sample was the highest and this sample contained much more spins of oxygen-center radicals. We could presume the metal Zn had a greater effect on the formation of EPFRs, and was easier to induce the formation of radicals with a longer half-life period.

Emission and distribution of PCDD/Fs and CBzs from two co-processing RDF cement plants in China.

An analysis of the emission and distribution characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and chlorobenzenes (CBzs) from two cement kilns (CK1 and CK2) is done. Six measurements in CK1 showed an increase of PCDD/F emission from 76 to 97 pg I-TEQ/Nm(3) after feeding 10 ton/h RDF (refuse derived fuel). For CK2, the effect of increasing the RDF substitution rates from 0 to 21 t/h on the emission of PCDD/Fs was investigated. The correlation analysis indicated that replacing parts of the conventional fuel with RDF could not increase the emission of PCDD/Fs. Furthermore, the gas/particle partitions of PCDD/Fs and CBzs in stack gas were investigated, indicating that PCDD/Fs and CBzs were more associated in gas phase, especially for the lower chlorinated ones. Moreover, the bag filter fly ash was characterized by its particle distribution, XRD- and EDS-analysis. Additionally, the level of PCDD/Fs in outflowing fly ash escalates for smaller particle size. In order to evaluate the environmental effect on inhabitants, the levels of PCDD/Fs were also determined in samples of ambient air collected in the vicinity of CK2 (~200 m).

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.

Recycling ash into the first stage of cyclone pre-heater of cement kiln.

Fly ash collected from the bag filter could be recycled into the first stage of the cyclone pre-heater of the cement kiln, resulting in the possible enrichment of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). In this study, soxhlet fly ash (SFA) and raw meal (RM) were selected as the basis for the PCDD/F formation experiments. The levels of 2,3,7,8-PCDD/Fs formed on the SFA and RM were observed to be 2550pg/g (157pg I-TEQ/g) and 1142pg/g (55pg I-TEQ/g), respectively. While less 2,3,7,8-PCDD/Fs was detected when SFA was mixed with RM, suggesting that recycling cement kiln ash would not largely increase the concentration of PCDD/Fs in flue gas. Furthermore, the possible influencing factors on the PCDD/F formation were also investigated. The formation of 2,3,7,8-PCDD/Fs was up to 10,871pg/g (380pg I-TEQ/g) with the adding of CuCl2, which was much higher than the results of CuO and activated carbon. Most importantly, the homologue, congener and gas/particle distribution of PCDD/Fs indicated that de novo synthesis was the dominant PCDD/F formation pathway for SFA. Lastly, principal component analysis (PCA) was also conducted to identify the relationship between the compositions of reactant and the properties of PCDD/Fs produced.

Effects of bypass system on PCDD/F emission and chlorine circulation in cement kilns.

A bypass at the kiln inlet allows the effective reduction of alkali chloride cycles and thus perhaps affects the emission of PCDD/Fs. Effects of bypass system on PCDD/F emission and chlorine circulation were studied in two typical dry cement kilns with 5000 ton/day clinker capacity in China and named CK1 and CK2, respectively. Firstly, the emission level of PCDD/Fs with the operation of bypass system was estimated in CK1, to certify that bypass system has a perfect adaption to the cement kiln regarding the PCDD/F emission even with the refuse derived fuel (RDF) as the replacement of fuel. On the other hand, the operating conditions in the CK2 were scrutinised by monitoring the concentrations of SO2, NH3 and HCl. In addition, the characteristics of raw meal, clinker, bag filter ash and bypass ash were also investigated by Energy Dispersive Spectrometer (EDS), metal and chlorine analysis. The balance of chlorine showed that 18 % of the possible accumulated chlorine could be ejected from the cement kiln system when 2 % of kiln exhaust gas was extracted. Furthermore, the emission level of PCDD/Fs in the main flue gas also decreased from 0.037 ± 0.035 ng I-TEQ/Nm(3) to 0.019 ± 0.007 ng I-TEQ/Nm(3) with a reduction efficiency of 48.2 %. Most importantly, PCDD/F emission from the bypass system was proven to have rather minor effect on the total emission factor. The congener distributions of PCDD/Fs were also analysed in the flue gas and fly ash, before and after application of bypass system, to find cues to the formation mechanism.

Suppression of dioxins by S-N inhibitors in pilot-scale experiments.

S-N inhibitors like thiourea and sewage sludge decomposition gases (SDG) are relatively novel dioxins suppressants and their efficiencies are proven in numerous lab-scale experiments. In this study, the suppression effects of both thiourea and SDG on the formation of dioxins are systematically tested in a pilot-scale system, situated at the bypass of a hazardous waste incinerator (HWI). Moreover, a flue gas recirculation system is used to get high dioxin suppression efficiencies. Operating experience shows that this system is capable of stable operation and to keep gaseous suppressant compounds at a high and desirable molar ratio (S + N)/Cl level in the flue gas. The suppression efficiencies of dioxins are investigated in flue gas both without and with addition of S-N inhibitors. A dioxin reduction of more than 80 % is already achieved when the (S + N)/Cl molar ratio is increased to ca. 2.20. When this (S + N)/Cl molar ratio has augmented to 4.18 by applying suppressant recirculation, the residual PCDD/Fs concentration in the flue gas shrank from 1.22 to 0.08 ng I-TEQ/Nm(3). Furthermore, the congener distribution of dioxins is analysed to find some possible explanation or suppression mechanism. In addition, a correlation analysis between (S + N)/Cl molar ratios and PCDD/Fs is also conducted to investigate the chief functional compounds for dioxin suppression.

Distribution of PCDD/Fs in the fly ash and atmospheric air of two typical hazardous waste incinerators in eastern China.

Distribution of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) in the fly ash and atmospheric air of one medical waste incinerator (MWI) and one industrial hazardous waste incinerator (IHWI) plants were characterized. The PCDD/F concentrations of the stack gas (fly ash) produced from MWI and IHWI were 17.7 and 0.7 ng international toxic equivalent (I-TEQ)/Nm(3) (4.1 and 2.5 ng I-TEQ/g), respectively. For workplace air, the total concentrations of PCDD/Fs were 11.32 and 0.28 pg I-TEQ/Nm(3) (819.5 and 15.3 pg/Nm(3)). We assumed that the large differences of PCDD/F concentrations in workplace air were due to the differences in chlorine content of the waste, combustion conditions, and other contamination sources. With respect to the homologue profiles, the concentrations of PCDFs decreased with the increase of the substituted chlorine number for each site. Among all of the PCDD/F congeners, 2,3,4,7,8-PeCDF was the most important contributor to the I-TEQ value accounting for ca. 43 % of two sites. The gas/particle partition of PCDD/Fs in the atmosphere of the workplace in the MWI was also investigated, indicating that PCDD/Fs were more associated in the particle phase, especially for the higher chlorinated ones. Moreover, the ratio of the I-TEQ values in particle and gas phase of workplace air was 11.0. At last, the relationship between the distribution of PCDD/Fs in the workplace air and that from stack gas and fly ash was also analyzed and discussed. The high correlation coefficient might be a sign for diffuse gas emissions at transient periods of fumes escaping from the incinerator.

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.