Simultaneous removal of PCDD/Fs and mercury by activated carbon from a full-scale MSW incinerator in southeast China.

This study emphasized on the removal performance of polychlorinated-ρ-dibenzodioxins and dibenzofurans (PCDD/Fs) and mercury by different activated carbon injection (ACI) rates from a full-scale (700 t/d) MSW incinerator. The result exhibited that the emission standard of PCDD/Fs and mercury could be met when the ACI rate reached 50 mg/Nm3 and 30 mg/Nm3, respectively. Lower chlorinated PCDD/Fs and PCDFs showed higher removal efficiencies compared with highly chlorinated PCDD/Fs and PCDDs, which could be attributed to the larger competitiveness of highly volatile congeners in AC adsorption than the lower volatile ones. AC turned out to have different adsorption selectivity for CP-routes PCDD/Fs congeners, among which 1379-TCDD was preferred to be absorbed while others exhibited little or poor selectivity for AC adsorption. The removal efficiency of PCDD/Fs was positively correlated with ACI rate at 99% confidence interval with a linear relationship (R2 = 0.98). Also, the outlet concentration of mercury decreased with the increase of ACI rate in a nearly linear function (R2 = 0.96). These results will be meaningful for the rational use of AC for pollutants control.

Solidification of heavy metals and PCDD/Fs from municipal solid waste incineration fly ash by the polymerization of calcium carbonate oligomers.

Calcium carbonate oligomers are gel-state precursors that can be crystallized by low-temperature heat treatments to form an inorganic material with a monolithic and continuous structure, this material can effectively solidify/stabilize heavy metals in municipal solid waste incineration fly ash (MSWI FA). Calcium chloride addition achieves FA stabilization/solidification by the formation and polymerization of calcium carbonate oligomers. The effects of calcium, triethylamine (TEA), and water-washing pretreatment on the solidification of heavy metals by the polymer were studied. Consequently, as more calcium was added, the solidification improved. When the ratio of TEA/Ca2+ was increased from 2:1 to 3:1, the solidification efficiency of As and Cd increased, but it decreased when the ratio was continuously increased to 4:1. After the water-washing pre-treatment, the MSWI FA had a significantly improved solidification effect on the heavy metals, and the solidification efficiencies of zinc, copper, cadmium, chromium, lead, and arsenic were 81.9%, 90.0%, 93.5%, 91.8%, 99.6% and 95.5%, respectively. Additionally, the solidification efficiency of PCDD/Fs was 56.5%. The heavy metals and PCDD/Fs in MSWI FA solidified by physical adsorption, wrapping and chemical precipitation. The continuous calcium carbonate structure adsorbed and encased the MSWI FA, and the heavy metals in the MSWI FA were converted from a free state to carbonate precipitates through carbonation, and the carbonate precipitate was more likely to be physical solidification by calcium carbonate.

PCDD/Fs characteristics in flue gas and surrounding environment of iron and steel smelting industry.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) concentrations and distributions, emission factors and amounts, and ambient air and soil potential sources were investigated by collecting flue gas, ambient air, and soil samples from ten sintering furnaces and two electric arc furnaces of eight iron and steel smelting industries (ISSI) in China. In flue gas, the concentrations of PCDD/Fs ranged from 0.05 to 2.93 ng I-TEQ Nm-3 (mass, from 0.38 to 30.67 ng Nm-3), with an average of 0.42 ng I-TEQ Nm-3 (mass, 4.99 ng Nm-3), respectively. In ambient air, the concentrations ranged from 0.05 to 0.35 pg I-TEQ m-3 (mass, from 0.66 to 5.66 pg m-3), with an average of 0.20 pg I-TEQ m-3 (mass, 2.96 pg m-3), respectively. In surface soil, the concentrations ranged from 1.80 to 21.02 ng I-TEQ kg-1 (mass, from 34.29 to 836.00 ng kg-1), with an average of 5.82 ng I-TEQ kg-1 (mass, 252.10 ng kg-1), respectively. In deep soil, the concentrations ranged from 1.17 to 12.00 ng I-TEQ kg-1 (mass, from 56.83 to 1488.00 ng kg-1), with an average of 7.76 ng I-TEQ kg-1 (mass, 433.20 ng kg-1), respectively. Compared with emission limits for PCDD/Fs, the compliance was 78.9% in flue gas, 100% in ambient air, and 77.3% in soil. In congener profiles, the contributions of PCDFs were much higher than those of PCDDs in flue gas and ambient air, but the opposite was observed in soil. In ten sintering furnaces, the emission factors ranged from 22.11 to 901.22 ng I-TEQ t-1, with an average of 373.80 ng I-TEQ t-1, respectively. In two electric arc furnaces, the emission factors were 1667.52 and 894.96 ng I-TEQ t-1, with an average of 1281.24 ng I-TEQ t-1. According to both principal component analysis and hierarchical cluster analysis, all ambient air samples were affected by the emissions of PCDD/Fs from ISSIs, but to different degrees. However, the concentrations of PCDD/Fs in most soil samples were not influenced by the ISSI emissions.

Inhibition of polychlorinated dibenzo-p-dioxins and dibenzofurans by phosphorus-containing compounds in model fly ash.

Waste incineration is a preferred method in China to dispose the municipal solid waste, but controlling the production of highly toxic polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans effectively during incineration is both challenging and imperative. In this study, the suppression of PCDD/Fs by various phosphorus-containing compounds was explored, and the mechanisms responsible for the inhibition were studied in detail. The experiments took place in a lab-scale vertical tubular reactor at 350 °C under a simulated flue gas (12 vol% O2 in N2 flow), and both the off-gases and residues were collected for PCDD/Fs analysis. The scanning electron microscopy and energy-dispersive X-ray spectroscopy were used to characterize the reaction residues. The experimental results revealed that NH4H2PO4 and (NH4)2·HPO4 showed the highest inhibitory effect (57.2% and 57.3%, respectively) on the PCDD/Fs formation, followed by CaHPO4 with inhibition efficiency of 39.1%. In contrast, KH2PO4 and K2HPO4 barely inhibited the generation of the PCDD/Fs. The inhibitory effect of NH4H2PO4 and (NH4)2·HPO4 was similar to that of nitrogen-based inhibitors. At the same time, it was proven that the inhibitory activity of CaHPO4 might be due to the reaction of it with Cu2+ forming stable compounds.

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.

Hot rolling sludge incineration: Suppression of PCDD/Fs by spent anion exchange resins.

Steel industry is the main industrial source of 'dioxins', i.e. polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). These arise mainly in the off-gas from sintering plant, yet also other operations, such as continuous casting, and hot and cold rolling could generate albeit minor amounts of dioxins. In this contribution it is verified in how far the incineration of hot rolling sludge (HRS) could contribute to such emissions and, if so, how these could be suppressed at low cost. Spent anion exchange resin (SAER) appeared as a dioxins suppressant during combustion tests of hot rolling sludge in a bench-scale tubular furnace. The reduction efficiency (RE) of PCDD/F and I-TEQ-generation attained 91.1% and 90.2%, respectively, with the addition of 2.5wt.% resin, and the highest dioxins RE reached 97.8% with 10wt.% resin addition. The PCDD/PCDF ratio raised markedly when adding resin, indicating stronger suppression for PCDF- than for PCDD-formation. However, further research is still needed to establish the effect of resin on PCDD/F formation and inhibition during full-scale experiments. The off-gas released by sludge and resin co-combustion was also monitored and the residue analysed by Energy Dispersive Spectrometer (EDS); the results revealed that the SO2 concentration in the off-gas was higher during co-combustion than when burning HRS only. Likewise, the sulphur content in the combustion residue rises with resin addition. Still, the suggestion that suppression of PCDD/F formation should be ascribed to the poisoning of catalytic metal by S-containing compounds seems to be invalidated by the high initial S/Cl-ratio of HRS, even before SAER addition. These surprising findings were further analysed by a scrutiny of fingerprints obtained at the five distinct dosages tested. The relative amount of 2,3,7,8-PCDD/F was remarkably depressed by inhibitor addition and the relative importance of the chlorophenols route strongly expanded. Several reaction schemes, showing the results of further signature analysis are presented and are expected to throw more light on the mechanism of formation and its suppression.

Dioxins degradation and reformation during mechanochemical treatment.

Mechanochemical dechlorination and destruction of polychlorinated dibenzo-p-dioxins and -furans (PCDD/F) on fly ash from Municipal Solid Waste Incineration was tested with and without additives (CaO and CaO/aluminium powder). The first results disappointed because of obvious PCDD/F-reformation and a second test series was conducted after removing soluble salts (NaCl, KCl …) by thorough two-stage water washing. This second test series was successful and demonstrated good destruction results, especially with combined CaO/aluminium powder as additive. In a third test series salt was again added to the water-washed fly ash, and the first, poor results were largely reconstituted. For all tests a fairly complete (94 out of 136 congeners) isomer-specific analysis was conducted and analysed, allowing to differentiate between, e.g., 2,3,7,8-substituted PCDD/F and congeners formed following the chlorophenol route. The first became more important in the samples series Fly Ash, Milled Fly Ash, milling with added CaO, and milling with CaO/aluminium-addition. The second follow the opposite trend. This isomer-specific analysis will form the basis for further study using Principal Component Analysis.

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.