Effect of reducing agent on catalytic hydrodechlorination of aqueous-phase OCDD/F.

Removal/destruction of aqueous-phase octachlorodibenzo-p-dioxin (OCDD) and octachlorodibenzofuran (OCDF) via hydrodechlorination process (HDC) is experimentally evaluated over palladium/activated carbon (Pd/AC) catalyst. Pd catalyst is mainly used as active component for effectiveness in removing dioxin from wastewater. Studies on the removal of PCDD/Fs accomplished with HDC reaction in aqueous phase are limited and the influencing factors have not been clarified. In this study, high-concentration OCDD/F are selected as targets, and the effects of solvent and operating temperature on dechlorination efficiency are investigated via experimental tests. The results indicate that the highest hydrodechlorination efficiency is achieved with isopropanol as solvent. The OCDD/F removal efficiency achieved with the solution of 80% isopropanol is higher than that of 50% isopropanol, whereas the destruction efficiency of OCDD/F reveals the opposite trend. Generally, the removal and destruction efficiencies of PCDFs are higher than those of PCDDs. In addition, the activation energies of OCDD and OCDF are calculated with the Arrhenius equation as 24.8 and 23.1 kJ/mol, respectively. Stability tests are conducted with three cycles. Overall, the results indicate that a high performance (≥99%) can be achieved by combining hydrodechlorination with Pd/AC at a temperature range of 303-353 K, demonstrating that Pd/AC has good potential for removing PCDD/Fs from wastewater.

Adsorption behavior of 2, 3, 7, 8-tetrachlorodibenzo-p-dioxin on pristine and doped black phosphorene: A DFT study.

Polychlorinated dibenzo-p-dioxins (PCDDs) are highly toxic to humans. The search for novel and effective methods and materials for detecting or removing these gas pollutants is becoming more important and urgent. With its high specific surface area, abundance, and variety of potential applications, phosphorene has attracted much research interest. In this study, density functional theory was used to study the interactions between a doped phosphorene sheet and a tetrachlorodibenzo-p-dioxin (TCDD) molecule. The initial configurations of the TCDD and metallic (Ca or Ti) or nonmetallic (S and Se) dopants were investigated during the TCDD-phosphorene interaction study. Adsorption energy, isosurface of electron density difference, and density of states analysis were utilized to explore the interactions between TCDD and phosphorene. The results indicated that Ca dopant effectively improved the interaction between TCDD and phosphorene. Se dopant reduced the interaction between TCDD and phosphorene. Combining interactions between TCDD and the pristine, Ca-doped, and Se-doped phosphorenes, phosphorene could be a promising candidate for TCDD sensing and removal.

Treatment technologies used for the removal of As, Cr, Cu, PCP and/or PCDD/F from contaminated soil: A review.

The contamination of soils by metals such as arsenic, chromium, copper and organic compounds such as pentachlorophenol (PCP) and dioxins and furans (PCDD/F) is a major problem in industrialized countries. Excavation followed by disposal in an appropriate landfilling is usually used site to manage these contaminated soils. Many researches have been conducted to develop physical, biological, thermal and chemical methods to allow the rehabilitation of contaminated sites. Thermal treatments including thermal desorption seemed to be the most appropriate methods, allowing the removal of more than 99.99% of organic contaminants but, they are ineffective for inorganic compounds. Biological treatments have been developed to remove inorganic and hydrophobic organic contaminants but their applications are limited to soils contaminated by easily biodegradable organic compounds. Among the physical technologies available, attrition is the most commonly used technique for the rehabilitation of soils contaminated by both organic and inorganic contaminants. Chemical processes using acids, bases, redox agents and surfactants seemed to be an interesting option to simultaneously extract organic and inorganic contaminants from soils. This paper will provide an overview of the recent developments in the field of decontamination technologies applicable for the removal of As, Cr, Cu, PCP and/or PCDD/F from contaminated soils.

QuEChERS extraction for multi-residue analysis of PCBs, PAHs, PBDEs and PCDD/Fs in biological samples.

In this study, a fast and rugged method is presented for the analysis of PCBs, PAHs, PBDEs and PCDD/Fs in biological tissues using a simple Quick, Easy, Cheap, Efficient, Rugged and Safe (QuEChERS) extraction and a clean-up by Gel Permeation Chromatography (GPC) and silica Solid Phase Extraction (SPE). Development was performed on blue mussels (Mytilus edulis) and Atlantic salmon (Salmo salar) for evaluation of two ranges of lipid and water content of biological tissues. Statistical validation was performed with Atlantic salmon samples. Forty-five PAHs were analyzed including the priority list of the US EPA and the European Union with 41 PCBs, 24 PBDEs and 17 PCDD/Fs. Instrumental analyses were performed on Gas Chromatography - High Resolution Mass Spectrometry (GC-HRMS). Accuracy was evaluated for PCBs and PCDD/Fs with a certified reference material furnished by the National Research Council Canada (NRCC) and also compared with results obtained by the conventional Soxhlet extraction. Statistical validation showed recoveries for PCBs, PAHs, PBDEs and PCDD/Fs close to 100% with average Relative Standard Deviation (RSD) lower than 10% and internal standard recoveries in the range of 70% with average RSD ranging from 5-15%. Average calculated Method Detection Limits (MDLs) were lower than 0.05µg/Kg for PCBs, 0.2µg/Kg for PAHs and PBDEs and 1ng/Kg for PCDD/Fs. The method is a faster and cheaper alternative to the time-consuming conventional method that has been used in most environmental laboratories.

Fast extraction of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran in sewage sludge and soil samples.

The current environmental legislations recommend monitoring chemical contaminants such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans before the use of sewage sludge on the agricultural land. In this study, a solid-liquid extraction with low-temperature purification (SLE-LTP) was optimized and validated to determine 2,3,7,8-tetrachlorodibenzo-p-dioxin and 2,3,7,8-tetrachlorodibenzofuran in sewage sludge and soil samples. The analyses were performed by gas chromatography-mass spectrometry operating in the selective ion mode (GC-MS-SIM). Acetonitrile:ethyl acetate 6.5:1.5 (v/v) was the best extraction phase, and the recoveries percentages were close to 100%. The linearity was demonstrated in the range of 1.25-25 µg L-1 of 1.25-20 µg L-1 for sewage sludge and soil, respectively. Matrix effect was proved for the two compounds and in the two matrices studied. Extraction percentages were between 78 and 109% and relative standard deviations ≤ 19%. The proposed method is faster than methods described in the literature because showed a few steps. The quantification limits (LOQ) in sewage sludge were 6.4 and 32 ng TEQ kg-1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. In soil, LOQs were 0.8 and 8.0 ng TEQ kg-1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. These values are lower than the maximum residue limits established by European Legislation. The method was applied to 22 agricultural soil samples from different Brazilian cities and 2,3,7,8-TCDF was detected in one of these samples.

Catalytic hydrodechlorination of PCDD/Fs from condensed water with Pd/γ-Al2O3.

A continuous pyrolysis system (CPS) with effective air pollution control devices (APCDs) is designed and constructed to remediate the soil containing high-concentration PCDD/Fs. The quench tower of the APCDs system can capture the pollutants of high boiling points from the flue gas of CPS and produces condensed water of high PCDD/Fs concentration (16-44 ng I-TEQ/L), and needs further treatment. First, the result of activated carbon adsorption test displays the PCDD/Fs toxicity concentration of effluents meet the regulatory standards as the liquid to solid ratio is controlled at 3: 1. However, large amount of activated carbon need to achieve the high removal efficiency leads to high cost, so catalytic hydrodechlorination technology with Pd/Al2O3 as catalyst is applied to treat the condensed water. The PCDD/Fs mass removal efficiency achieved without the reducing agent is 53.21% with the operating time of 180 min. As 5% reducing agent (methanol) is added, the removal efficiency increases to 71.86%. In addition, to better understand the differences between molecular hydrogen and hydrogen donor, the condensed water was pre-aerated with hydrogen and catalytic hydrodechlorination test with palladium as catalyst was conducted. The results show that the PCDD/Fs mass removal efficiency increases to 97.34% with the operating time of 180 min, demonstrating the high PCDD/Fs removal efficiency of catalytic hydrodechlorination.

Dual degradation of gaseous 1,2-dichlorobenzene and PCDD/Fs using Ce doped VxOy/TiO2 immobilized on cordierite.

The photocatalytic film Ce doped VxOy/TiO2 was loaded on cordierite honeycomb (CHC), and this composite was prepared by sol-gel and dipping method, with Ce, oxides of V and TiO2 as dopant and key substances, respectively. Using gaseous 1,2-dichlorobenzene to replace dioxin as target pollutant, dual degradation experiments at 140-280 °C were carried out (thermal decomposition and photodegradation), and the effects of preparation conditions on catalytic activity were investigated: doping amount of Ce, dipping time in the gel, the concentration of ammonium metavanadate (NH4VO3) solution, dipping time in NH4VO3 solution, sintering temperature. The gaseous samples were taken before and after the reactor and analyzed by gas chromatography. According to the results, the optimal preparation conditions were determined, and the corresponding removal rate was above 95% after 90 min of degradation at 280 °C. The composite was examined by ultrasonic to analyze the adhesive strength between the film and CHC, and further characterized by XRD and SEM. Furthermore, flue gas from waste incinerator was chosen as target pollutant, which contained PCDD/Fs, the industrial sidestream degradation experiment was carried out and showed excellent removal efficiency of the composite, the removal rate of PCDD/Fs reached ca. 90% after 90 min of degradation.

Adsorption of polychlorinated dibenzo-p-dioxins/dibenzofurans on activated carbon from hexane.

Activated carbon is widely used to abate dioxins and dioxin-like compounds from flue gas. Comparing commercial samples regarding their potential to adsorb dioxins may proceed by using test columns, yet it takes many measurements to characterise the retention and breakthrough of dioxins. In this study, commercial activated carbon samples are evaluated during tests to remove trace amounts of dioxins dissolved in n-hexane. The solution was prepared from fly ash collected from a municipal solid waste incinerator. The key variables selected were the concentration of dioxins in n-hexane and the dosage of activated carbon. Both polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) showed very high removal efficiencies (94.7%-98.0% for PCDDs and 99.7%-99.8% for PCDFs). The presence of a large excess of n-hexane solvent had little effect on the removal efficiency of PCDD/Fs. The adsorbed PCDD/Fs showed a linear correlation (R(2) > 0.98) with the initial concentrations. Comparative analysis of adsorption isotherms showed that a linear Henry isotherm fitted better the experimental data (R(2) = 0.99 both for PCDDs and PCDFs) than the more usual Freundlich isotherm (R(2) = 0.88 for PCDDs and 0.77 for PCDFs). Finally, the results of fingerprint analysis indicated that dioxin fingerprint (weight proportion of different congeners) on activated carbon after adsorption did not change from that in hexane.

Thermal desorption of PCBs from contaminated soil with copper dichloride.

Copper dichloride is an important catalyst both in the dechlorination of chlorinated aromatic compounds and the formation of PCDD/Fs. The effect of copper dichloride on polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) was studied in treated soil and off gas after thermal desorption of PCB-contaminated soil at 300, 400, 500, 600 °C. The presence of copper dichloride clearly enhances thermal desorption by promoting PCBs removal, destruction, and dechlorination. After thermal treatment at 600 °C for 1 h, the removal efficiency and destruction efficiency for PCBs reached 98.1 and 93.9%, respectively. Compared with the positive influence on PCBs, copper dichloride catalyzed large amount of PCDFs formation at 300 °C, with the concentration ratio of 2.35. The effect of CuCl2 on PCDFs formation weakened with the rising temperature since PCDFs destruction became dominant under higher temperature. Different from PCDFs, PCDDs concentration in treated soil and off gas decreased continuously with the increasing temperature.

Removal of PCBs and HCB from contaminated solids using a novel successive self-propagated sintering process.

Thermal treatments are the primary technologies used to remove persistent organic pollutants from contaminated solids. The high energy consumption during continuous heating, required cost for treating the exhaust gas, and potential formation of secondary pollutants during combustion have prevented their implementation. A novel successive self-propagated sintering process was proposed for removing polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) from contaminated solids in a low-cost and environmentally friendly way. Nine laboratory-scale experiments involving different initial concentrations of pollutants and solid compositions were performed. Almost all PCBs (>99%) and HCB (>97%) were removed from solids under constant experimental conditions. Varying initial concentrations of PCBs and HCB in the contaminated solids did not influence the removal efficiency of the pollutants; however, the degradation efficiency of pollutants increased as their initial concentrations increased. Although varying levels of PCDD/Fs were detected in the effluent gas, they were all within the emission standard limit.

Removal efficiencies for 136 tetra- through octa-chlorinated dibenzo-p-dioxins and dibenzofuran congeners with activated carbons.

In this study, the removal efficiency of 136 tetra- to octa-chlorinated dibenzo-p-dioxin (CDD)/furan (F) congeners from a nitrogen + oxygen carrier gas was studied using a laboratory-scale, fixed bed adsorption system. Two kinds of activated carbon with dissimilar pore structures were used as adsorbents. The total concentration of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) in the source gas was 541 ng/Nm(3) and that of the 17 toxic 2,3,7,8-substituted PCDD/Fs 96.35 ng/Nm(3), accounting for 17.8% of the total original weight amount. Their toxic equivalent quantity (TEQ) was 8.31 ng I-TEQ/Nm(3). For both activated carbons, the removal efficiencies of the ten PCDD/F homologue groups rise with chlorine substitution number. The removal efficiencies vary approximately as a power function of vapor pressure (correlation coefficients r(2) = 0.93 and 0.81, respectively). Competitive adsorption and desorption occur as adsorption time went on, causing elution of the lower chlorinated homologues, i.e. tetra-CDD/F and Penta-CDD/F congeners. In addition, there are significantly different concentration distributions for isomers in the same homologue groups. However, their removal efficiencies have weak correlation with their initial concentrations. The correlation coefficients are from -0.47 to 0.32 and from -0.57 to 0.46 respectively for the two kinds of activated carbons.

Simultaneous removal of PCDD/Fs and NOx from the flue gas of a municipal solid waste incinerator with a pilot plant.

The pilot-scale plant on the simultaneous removal of PCDD/Fs and NOx from the flue gas of a municipal solid waste incinerator is presented. In order to research the influence of temperature on the catalytic decomposition of PCDD/Fs and the selective catalytic reduction of NOx, the experiments were performed at 220 °C, 260 °C, and 300 °C, and the congener profiles of PCDD/Fs for the samples collected at the inlet and outlet were illustrated. Noteworthy, the detailed congener distributions of PCDD/Fs in the gas-phase and particle-phase of the inlet and 300-outlet (decomposition temperature = 300 °C) samples are presented, and the removal efficiencies η(g-I-TEQ) and η(p-I-TEQ) reached to 94.94% and 99.67%, respectively. The effect of the SCR process on the removal of PCDD/Fs was also studied at a relatively low temperature of 220 °C. Additionally, the NOx emissions and the SCR efficiencies were investigated.

Effect of oxygen content on the thermal desorption of polychlorinated biphenyl-contaminated soil.

Oxygen plays an important role during the thermal treatment of soil, contaminated with polychlorinated biphenyls (PCBs), due to the potential oxidation of PCBs to form polychlorinated dibenzofurans (PCDFs). The effect of oxygen content (0, 5, 21 and 100%) in carrier gases on PCBs and PCDD/Fs was studied both in soil and gas after thermal desorption of PCBs contaminated soil at 500 °C. All 209 congeners of PCBs and 136 congeners of PCDD/Fs (P = 4 to 8) were analysed. Oxygen content showed little effect on PCB removal and destruction. Under different carrier gases, the removal efficiency and the destruction efficiency for PCBs attained 93.8-95.5 and 83.0-85.0 %, respectively. The levels of PCDD/Fs in soil and gas were correlated positively with oxygen content. Compared with PCDDs, PCDFs in soil were not effectively removed under oxidative conditions because there was chemistry going on and PCBs were being converted to PCDFs. The total concentration of PCDFs in soil and gas was 2.6, 11.3, 15.6 and 17.5 times of the initial PCDFs concentration (21.9 ng/g) in raw soil with increasing oxygen content. Thus, substantial amounts of PCDFs were generated in the presence of oxygen during the treatment of contaminated soil.

Comparison of adsorption behavior of PCDD/Fs on carbon nanotubes and activated carbons in a bench-scale dioxin generating system.

Porous carbon-based materials are commonly used to remove various organic and inorganic pollutants from gaseous and liquid effluents and products. In this study, the adsorption of dioxins on both activated carbons and multi-walled carbon nanotube was internally compared, via series of bench scale experiments. A laboratory-scale dioxin generator was applied to generate PCDD/Fs with constant concentration (8.3 ng I-TEQ/Nm(3)). The results confirm that high-chlorinated congeners are more easily adsorbed on both activated carbons and carbon nanotubes than low-chlorinated congeners. Carbon nanotubes also achieved higher adsorption efficiency than activated carbons even though they have smaller BET-surface. Carbon nanotubes reached the total removal efficiency over 86.8 % to be compared with removal efficiencies of only 70.0 and 54.2 % for the two other activated carbons tested. In addition, because of different adsorption mechanisms, the removal efficiencies of carbon nanotubes dropped more slowly with time than was the case for activated carbons. It could be attributed to the abundant mesopores distributed in the surface of carbon nanotubes. They enhanced the pore filled process of dioxin molecules during adsorption. In addition, strong interactions between the two benzene rings of dioxin molecules and the hexagonal arrays of carbon atoms in the surface make carbon nanotubes have bigger adsorption capacity.

Decontamination of metals, pentachlorophenol, and polychlorined dibenzo-p-dioxins and dibenzofurans polluted soil in alkaline conditions using an amphoteric biosurfactant.

In this paper, flotation in acidic conditions and alkaline leaching soil washing processes were compared to decontaminate four soils with variable contamination with metals, pentachlorophenol (PCP), and polychlorodibenzo dioxins and furans (PCDD/F). The measured concentrations of the four soils prior treatment were between 50 and 250 mg/kg for As, 35 and 220mg/kg for Cr, 80 and 350mg/kg for Cu, and 2.5 and 30mg/kg for PCP. PCDD/F concentrations reached 1394, 1375, 3730, and 6289ng/kg for F1, S1, S2, and S3 soils, respectively. The tests were carried out with masses of 100g of soil (fraction 0-2 mm) in a 2 L beaker or in a 1 L flotation cell. Soil flotation in sulphuric acid for 1 h at 60 degreeC with three flotation cycles using the surfactant cocamidopropyl betaine (BW) at 1% allows the solubilization of metals and PCP with average removal yields of 85%, 51%, 90%, and 62% for As, Cr, Cu, and PCP, respectively. The alkaline leaching for 2 h at 80 degreeC solubilizes As, Cr, Cu, and PCP with average removal yields of 60%, 32%, 77%, and 87%, respectively. Tests on PCDD/F solubilization with different surfactants were carried out in combination with the alkaline leaching process. PCDD/F removal yields of 25%, 72%, 70%, and 74% for F1, S1, S2, and S3 soils, respectively, were obtained using the optimized conditions.

Comprehensive profiling of 136 tetra- to octa-polychlorinated dibenzo-p-dioxins and dibenzofurans using ionic liquid columns and column combinations.

The orders of elution of all 136 tetra- to octa-chlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were determined on six gas chromatography (GC) columns. Three of these columns had ionic liquid stationary phases (SLB-IL111, SLB-IL76 and SLB-IL61; Supelco), one a liquid crystal phase (LC-50; Restek), one a chiral phase (ßDEXcst; Restek) and one a low bleed non-polar phase (DB-XLB; J&W/Agilent). According to our results, the high polarity and multiple solvation interactions of the ionic liquid stationary phases offered superior resolving power to that achieved with previously evaluated columns. The SLB-IL61 and SLB-IL111 columns resolved or partially separated 106 and 100 congeners, respectively, of the 136 PCDD/Fs. The SLB-IL61 also resolved 15 and partially separated one of the seventeen 2,3,7,8-substituted PCDD/Fs. Additional congeners can be separated by complementary analyses using additional columns in a dual- or triple-column approach. For example, using a combination of the SLB-IL61 and SLB-IL111 columns all but 8 congeners would be separated, including all 2,3,7,8-substituted PCDD/Fs. Two more congeners would be separated using a combination of SLB-IL76 and a liquid crystal (SB-Smectic) column, but in this case the 2,3,7,8-TeCDF would not be resolved. Three-column combinations would give even better separation: the DB-17/Smectic/SLB-IL76 and DB-225/Smectic/SLB-IL111 combinations would separate all but 1 of the 136 PCDD/F congeners. Unfortunately, the smectic column is no longer in production. If only commercially available columns are considered, combinations of SLB-IL61 and SLB-IL111 with DB-XLB, LC-50, or DB-225 offer the best performance, with 4, 4, and 3 unresolved congeners, respectively. Moreover, in each of these cases, one of the congeners in each unresolved pair is resolved on at least one of the other columns and so a reasonable estimate of the unresolved congeners' concentrations can be obtained by subtraction. The profiling of all 136 PCDD/Fs is thus greatly facilitated by using ionic liquid columns or combinations including such columns. However, there is room for improvement in the technical performance of the evaluated ionic liquid columns: their long-term retention time stability was poor and some highly chlorinated and sterically hindered congeners underwent dehalogenation during separation.

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.

Determination of polychlorinated biphenyls and polychlorinated dibenzo-p-dioxins and dibenzofurans by pressurized liquid extraction and gas chromatography coupled to mass spectrometry in street dust samples.

Owing to massive pollution with polychlorinated biphenyls in the harbour area of Dortmund (Germany), several dust samples were taken from surfaces at industrial sites and analyzed by the North-Rhine Westphalian State Agency for Nature, Environment, and Consumer Protection (LANUV NRW). This report describes and validates a rapid approach to screening for the presence of polychlorinated biphenyls (PCBs) in street dust. Samples were collected by using a natural bristle brush and stainless steel scoops. Mass recovery of fine-particle sea sand (a dust surrogate) on asphalt and concrete surfaces was used as a criterion for the effectiveness of sampling. Better recoveries of sea sand were achieved on concrete than on asphalt surfaces. Furthermore, temperature optimization for a pressurized liquid extraction (PLE) method used to extract PCBs and polychlorinated dibenzodioxins and polychlorinated furans (PCDD/Fs) from street dust samples was developed and compared with Soxhlet extraction for the analysis of PCBs in real street dust samples. Toluene was used as the extraction solvent in both cases. During this study, a combination of toluene and PLE achieved better extraction efficiencies than Soxhlet extraction. Finally, the performance of the PLE method was evaluated by analysing NIST Standard Reference Material 1649a for PCB and PCDD/F concentrations. This demonstrated that the accuracy of the PLE method for the determination of both substance classes was satisfactory. In addition, concentrations of PCBs and PCDD/Fs in street dust samples from industrial sites are reported.

Reduction of PCDDs/PCDFs in MSWI fly ash using microwave peroxide oxidation in H2SO4/HNO3 solution.

Microwave peroxide oxidation (MPO) is an energy-efficient and low GHG emission technology to destroy the hazardous organic compounds in solid waste. The objective of this paper is to explore the reduction feasibility of PCDDs/Fs in MSWI fly ash using the MPO in H2SO4/HNO3 solution. Nearly all PCDDs/Fs, 99% in the original fly ash, can be reduced in 120min at the temperature of 150°C using the MPO treatment. It was also found that a change occurred in the content distribution profiles of 17 major PCDD/F congeners before and after MPO treatment. This provides the potential to reduce the actual PCDDs/Fs content more than I-TEQ contents of PCDDs/Fs. The percentile distribution profile has a tendency of higher chlorinated PCDDs/Fs moving to the lower ones. It concludes that a significant reduction efficiency of I-TEQ toxicity was achieved and showed sufficient reduction of toxic level to lower than 1.0ngI-TEQ(gdw)(-1). The treatment temperature would be a critical factor facilitating the dissolution because higher temperature leads more inorganic salt (parts of fly ash) dissolution. Some problems caused by the MPO method are also delineated in this paper.

Removal of carbon constituents from hospital solid waste incinerator fly ash by column flotation.

Hospital solid waste incinerator (HSWI) fly ash contains a large number of carbon constituents including powder activated carbon and unburned carbon, which are the major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in fly ash. Therefore, the removal of carbon constituents could reduce PCDD/Fs in fly ash greatly. In this study, the effects of the main flotation parameters on the removal of carbon constituents were investigated, and the characteristics of the final product were evaluated. The results showed that loss on ignition (LOI) of fly ash increased from 11.1% to 31.6% during conditioning process. By optimizing the flotation parameters at slurry concentration 0.05 kg/l, kerosene dosage 12 kg/t, frother dosage 3 kg/t and air flow rate 0.06 m(3)/h, 92.7% of the carbon constituents were removed from the raw fly ash. Under these conditions, the froth product has LOI of 56.35% and calorific values of 12.5 MJ/kg, LOI in the tailings was below 5%, and the total toxic equivalent (TEQ) of PCDD/Fs decreased from 5.61 ng-TEQ/g in the raw fly ash to 1.47 ng-TEQ/g in the tailings. The results show that column flotation is a potential technology for simultaneous separation of carbon constituents and PCDD/Fs from HSWI fly ash.