Thermal degradation of PCDD/F in municipal solid waste ashes in sealed glass ampules

Due to their high concentrations of toxic organic compounds such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), metals, and water-soluble salts, fly ashes are classified as hazardous waste in the European Union and are required to be deposited in controlled landfills. We have shown here that the tetra- to octachlorinated PCDD/F in fly ash can be degraded by thermal treatment. The temperature needed for total degradation of PCDD/F depends on the composition of the fly ash. Its concentrations of unburned carbon and alkaline compounds were found to be important in this respect. Experimental design was used to investigate the effects of varying the temperature, residence time, and atmosphere on the degradation of PCDD/F in three different types of fly ash. The results showed that the three ashes clearly showed different degradation potentials for PCDD/F during thermal treatment. The concentrations of unburned carbon, alkaline species such as CaO and Na2O, and metals such as copper and iron strongly influenced the degradation of PCDD/F. However, the different combinations of pH and amounts of native PCDD/F, unburned carbon, metals (Cu, Fe, Sn and Na), and sulfur in the ashes made it difficult or even impossible to conclude that any single parameter was responsible for the degradation of PCDD/F in these thermal treatment experiments. The decreases observed in all of the experiments are due to dechlorination and/or destruction of PCDD/F: depending on the temperature and ash composition, either of these processes may be the more important.     

De novo synthesis of polychlorinated dibenzo-p-dioxins and dibenzofurans on fly ash from a sintering process

Fly ash, collected in the electrostatic precipitator of a sinter plant in Belgium, has been examined and characterized in terms of its behavior with respect to thermal polychlorodibenzo-p-dioxins (PCDD) and polychlorodibenzofurans (PCDF) formation. Thermal experiments of the fly ash were conducted in a flow of air. The temperature was varied from 250 to 450 degrees C, and the reaction time varied from 30 min to 6 h. For comparison, the oxidative degradation of carbon in the fly ash was studied by differential scanning calorimetry (DSC) in the temperature range from 50 to 500 degrees C. Besides the known maximum of formation of PCDD/Fs around 325 degrees C generally found on experiments with incinerator fly ash, a second maximum of formation around 400 degrees C is observed on the sinter fly ash used in this study. DSC measurements on the fly ash show that the oxidative degradation of carbon appears at these two different temperatures confirming that the de novo synthesis on this kind of fly ash take place at two different optimum temperatures. About the reaction time, already after 30 min, an important quantity of PCDD/Fs is formed; the fast increase in PCDD/Fs amount is followed by a slower formation rate between 2 and 4 h. At longer reaction time, the formation slows down, and decomposition reactions become important. Analysis of homologue distribution indicates that the profile of PCDD/Fs is independent of the reaction time but that an increase of the temperature leads to a rise of lower chlorinated species. In all experiments, PCDF are formed preferentially (total PCDF/PCDD ratios larger than 5). The PCDF/PCDD ratio is clearly independent of the reaction time. Concerning the temperature, the apparently better stability of PCDF at high temperature (PCDF/PCDD ratio higher at high temperature) results in the fact of different PCDF/PCDD ratios for the different family and modifications of homologue distribution with the temperature. The isomer distribution shows little reaction time or temperature dependency, which is an argument in favor of a thermodynamic control of the isomer distribution during de novo formation of PCDD/Fs. Differences within the isomer distribution patterns of PCDD/Fs obtained from the laboratory de novo synthesis experiments and the original fly ash, reflecting the formation under the industrial process, suggest a different mechanism of formation in the sinter plant for the PCDD and PCDF. The de novo synthesis is sufficient to explain the PCDF formation in the real process, but synthesis from precursors must play a role for the PCDD formation.     

Advanced oxidation of caffeine in water: on-line and real-time monitoring by electrospray ionization mass spectrometry

High performance liquid chromatography (HPLC), ultraviolet spectroscopy (UV), and total organic carbon (TOC) analyses show that caffeine is quickly and completely degraded underthe oxidative conditions of the UV/H2O2,TiO2/ UV, and Fenton systems but that the organic carbon content of the solution decreases much more slowly. Continuous on-line and real-time monitoring by electrospray ionization mass (ESI-MS) and tandem mass spectrometric experiments (ESI-MS/MS) as well as high accuracy MS measurements and gas chromatography-mass spectrometry analysis show that caffeine is first oxidized to N-dimethylparabanic acid likely via initial OH insertion to the C4=C8 caffeine double bond. A second degradation intermediate, di(N-hidroxymethyl)parabanic acid, has been identified by ESI-MS and characterized by ESI-MS/MS and high accuracy mass measurements. This polar and likely relatively unstable compound, which is not detected by off-line GC-MS analysis, is likely formed via further oxidation of N-dimethylparabanic acid at both of its N-methyl groups and constitutes an unprecedented intermediate in the degradation of caffeine.     

Application of solid ash based catalysts in heterogeneous catalysis

Solid wastes, fly ash, and bottom ash are generated from coal and biomass combustion. Fly ash is mainly composed of various metal oxides and possesses higher thermal stability. Utilization of fly ash for other industrial applications provides a cost-effective and environmentally friendly way of recycling this solid waste, significantly reducing its environmental effects. On the one hand, due to the higher stability of its major component, aluminosilicates, fly ash could be employed as catalyst support by impregnation of other active components for various reactions. On the other hand, other chemical compounds in fly ash such as Fe2O3 could also provide an active component making fly ash a catalyst for some reactions. In this paper, physicochemical properties of fly ash and its applications for heterogeneous catalysis as a catalyst support or catalyst in a variety of catalytic reactions were reviewed. Fly-ash-supported catalysts have shown good catalytic activities for H2 production, deSO(x), deNO(x), hydrocarbon oxidation,and hydrocracking, which are comparable to commercially used catalysts. As a catalyst itself, fly ash can also be effective for gas-phase oxidation of volatile organic compounds, aqueous-phase oxidation of organics, solid plastic pyrolysis, and solvent-free organic synthesis.     

Photocatalytic atrazine degradation by synthetic minerals,atmospheric aerosols,and soil particles

In this work, the photocatalytic atrazine degradation by seven synthetic minerals and five environmental particle samples was examined to investigate a possible contribution of photocatalysis to the abiotic degradation of atrazine in the environment. Particle suspensions containing 500 ng/L atrazine were irradiated with a sun simulator, and the atrazine degradation was monitored by enzyme-linked immunosorbent assay (ELISA). Atrazine detection by ELISA proved to be an useful analytical tool because of low cross-reactivity of atrazine metabolites and high sensitivity with detection limits in the lower nanograms per liter range. The atrazine degradation followed first-order kinetics, and the obtained rate coefficients were compared with the rate of direct photolysis. Known photocatalysts, such as TiO2 and ZnO, showed the expected fast photocatalytic degradation (k = 27-327 x 10(-3) min(-1)) of atrazine. The degradation rates detected upon irradiation of titanium-, zinc-, or iron-containing minerals were orders of magnitudes lower (k = 0.15-0.70 x 10(-3) min(-1)) but still significantly faster than direct photolysis without particles (k = 0.10 x 10(-3) min(-1)). With environmental particle samples (soot, fly ash, sand, road dust, and volcanic ash), however, no significant photocatalytic activity was observed (k = 0.07-0.16 x 10(-3) min(-1)). The atrazine degradation rates were in the range of direct photolysis. Thus photocatalysis by aerosol or soil particles appears not to enhance abiotic atrazine degradation in the environment.     

铁改性聚丙烯腈纳微米纤维催化剂在偶氮染料降解中的应用

利用静电纺丝法制备聚丙烯腈（PAN）纳米纤维,应用偕胺肟改性PAN纳米纤维（AO-n-PAN）与FeCl3反应得到PAN纳米纤维铁配合物（Fe-AO-n-PAN）,并使用SEM和FTIR对其进行表征。最后将Fe-AO-n-PAN作为非均相光催化剂应用于偶氮染料C.I.活性红195（RR 195）的氧化降解反应中;考察催化剂中铁离子含量（QFe-PAN）,辐射光强度和H2O2初始浓度等因素对其催化活性的影响,并使用紫外可见光谱和总有机碳（TOC）对染料的氧化降解反应进行分析。结果表明：AO-n-PAN中的偕胺肟基团与铁离子发生配位反应,增加AO-n-PAN中的偕胺肟基团数目能制备出高QFe-PAN的Fe-AO-n-PAN。Fe-AO-n-PAN中QFe-PAN的增加和辐射光强度的增大都可以显著提高RR 195的降解速率,当H2O2为3.0 mmol/L时Fe-AO-n-PAN催化活性较高。Fe-AO-n-PAN不仅对染料分子中的偶氮键和芳香环结构具有催化作用,而且还能够使其转化为无机物。     

Speciation of zinc in municipal solid waste incineration fly ash after heat treatment: an X-ray absorption spectroscopy study

Fly ash is commonly deposited in special landfills as it contains toxic concentrations of heavy metals, such as Zn, Pb, Cd, and Cu. This study was inspired by our efforts to detoxify fly ash from municipal solid waste incineration by thermal treatment to produce secondary raw materials suited for reprocessing. The potential of the thermal treatment was studied by monitoring the evaporation rate of zinc from a certified fly ash (BCR176) during heating between 300 and 950 degrees C under different carrier gas compositions. Samples were quenched at different temperatures for subsequent investigation with X-ray absorption spectroscopy (XAS). The XAS spectra were analyzed using principal component analysis (PCA), target transformation (TT), and linear combination fitting (LCF) to analyze the major Zn compounds in the fly ash as a function of the temperature. The original fly ash comprised about 60% zinc oxides mainly in the form of hydrozincite (Zn5(OH)6(CO3)2) and 40% inerts like willemite (Zn2SiO4) and gahnite (ZnAl2O4) in a weight ratio of about 3:1. At intermediate temperatures (550-750 degrees C) the speciation underlines the competition between indigenous S and Cl with solid zinc oxides to form either volatile ZnCl2 or solid ZnS. ZnS then transformed into volatile species at about 200 degrees C higher temperatures. The inhibiting influence of S was found absent when oxygen was introduced to the inert carrier gas stream or chloride-donating alkali salt was added to the fly ash.     

蛇莓果实花色苷的稳定性及其降解动力学

探究蛇莓果实花色苷在多种条件下的稳定性及降解动力学。采用pH示差法测定不同pH值、温度、光照强度、氧化剂、还原剂、金属离子对花色苷稳定性的影响。研究表明,不同pH条件下蛇莓果实花色苷热降解符合一级动力学模型,花色苷在强酸性条件下的稳定性高于弱酸和中性条件;蛇莓果实花色苷的热稳定性较差,随着环境温度升高,降解速率k增大,半衰期和递减时间D值缩短,pH值2.0时活化能最大为68.65 kJ/mol,pH值5.0时活化能最小为42.35 kJ/mol,其降解为吸热非自发反应;6 000 lx光照和H2O2均会加快蛇莓果实花色苷的降解,且花色苷在光照和H2O2条件下降解均符合一级动力学模型,在光照条件下的降解速率为 0.012 3 d-1,半衰期56.35 d,H2O2条件下降解速率随H2O2体积分数的升高而增大;质量分数0.20%的Na2SO3对蛇莓果实花色苷的降解有抑制作用;Na+、K+对蛇莓果实花色苷无影响,而Al3+、Cu2+、Fe3+可显著破坏蛇莓果实花色苷的稳定性。综上,蛇莓果实花色苷应尽量在酸性、低温、避光且无氧化剂及Fe3+的条件下生产加工,以避免大量降解。     

Gaseous mercury from curing concretes that contain fly ash: laboratory measurements

Total gaseous mercury in headspace air was measured for enclosed concretes dry curing at 40 degrees C for intervals of 2, 28, and 56 days. Release of mercury was confirmed for ordinary Portland cement concrete (OPC) and three concretes in which class F fly ash substituted for a fraction of the cement: (a) 33% fly ash (FA33), (b) 55% fly ash (FA55), and (c) 33% fly ash plus 0.5% mercury-loaded powdered activated carbon (HgPAC). Mean rates of mercury release (0.10-0.43 ng/day per kg of concrete) over the standard first 28 days of curing followed the order OPC < FA33 approximately FA55 < HgPAC. The mercury flux from exposed surfaces of these concretes ranged from 1.9 +/- 0.5 to 8.1 +/-2.0 ng/m(2)/h, values similar to the average flux for multiple natural substrates in Nevada, 4.2 +/- 1.4 ng/m(2)/h, recently published by others. Air sampling extending for 28 days beyond the initial 28-day maturation for OPC, FA55, and HgPAC suggested that the average Hg release rate by OPC is constant over 56 days and that mercury release rates for FA55 and HgPAC may ultimately diminish to levels exhibited by OPC concrete. The release of mercury from all samples was less than 0.1% of total mercury content over the initial curing period, implying that nearly all of the mercury was retained in the concrete.     

Sonochemical decomposition of phenol: evidence for a synergistic effect of ozone and ultrasound for the elimination of total organic carbon from water

Advanced oxidation processes (AOPs) for water and wastewater treatment are often handicapped by their inability to completely eliminate total organic carbon (TOC). In order to explore the capability of the combination of ultrasonic irradiation with ozone for the rapid removal of TOC, we examined the degradation rates of dissolved phenol (C6H5OH) in water with high-frequency ultrasound over the range of 200-1000 kHz, with ozone and with the combined application of sonication and ozonation. When ozone and ultrasound are applied simultaneously, a pronounced synergistic effect is observed that leads to the complete and rapid elimination of TOC at enhanced reaction rates. At longer reaction times, phenol oxidation by 03 leads to oxalate and formate, which accounts for the majority of the residual TOC. However, the combination of US (ultrasound) and ozone together readily oxidizes HCO2- and C2O4(2-) to CO2 while they prove to be relatively resistant to further oxidation to CO2 by O3 alone.     

Dynamic change of copper in fly ash during de novo synthesis of dioxins

Although many researchers have reported that copper chloride is an important catalyst that generates relatively large amounts of dioxins in heat experiments involving model fly ash, details on the behavior of copper during the process are still unavailable. In this study, we used in situ XANES experiments involving one type of real fly ash, which originated from a municipal solid-waste incinerator (MSWI), and two fly ash models to investigate the behavior of copper in fly ash at temperatures that are suitable for de novo synthesis, which is the major formation route for dioxins during waste incineration and thermal processes. Cupric compounds in real fly ash and model fly ash A(CuCl2.2H2O + activated carbon (AC) + boron nitride (BN)) were reduced to cuprous compounds or elemental copper at low temperatures. The changes in the Cu XANES spectra of real fly ash were similar to those of model fly ash A and those of an oxychlorination catalyst. In model fly ash B (CuO + AC + KCl + BN), CuO did not vary dramatically in the temperature range studied. In this study, we found strong evidence that oxychlorination, the key mechanistic step in the formation of dioxins, occurred in both real MSWI and model fly ash.     

Occurrence and destruction of PAHs,PCBs, CIPhs,CIBzs, and PCDD/Fs in ash from gasification of straw

Two experiments were performed with an atmospheric circulating fluidized bed gasifier (ACFBG), the first with pelletized straw and the second with loose straw, to investigate the occurrence of polycyclic aromatic hydrocarbons (PAHs), chlorophenols (CIPhs), polychlorinated biphenyls (PCBs), polychlorinated benzenes (ClBzs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) in the bottom ash and fly ash formed during gasification. Only PAHs were present in large amounts, and only in the fly ash, ranging from 300 to 555 mg/kg ash in the tests with pelletized straw and from 73 to 118 mg/kg ash in those with loose straw. These amounts are so high that environmentally safe disposal or reuse of the ash would be difficult, so the development of a technique to handle the problem was included in the project. The method investigated was to burn the fly ash in a circulating fluidized bed (CFB) boiler in order to destroy the PAHs. This worked surprisingly well, eliminating 99% of the PAHs, without any further formation of the other harmful organic compounds analyzed. Thus, this method could actually be useful in practice. Especially the fact that the formation of PCDD/Fs was minimal during gasification and further treatment of the ash in the CFB boiler makes the gasification technique highly competitive relative to conventional combustion methods.     

Semiconductor-mediated Photocatalyzed degradation of a herbicide derivative, chlorotoluron, in aqueous suspensions

The photocatalytic degradation of a herbicide derivative, chlorotoluron [3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 1], has been investigated in aqueous suspensions of titanium dioxide (TiO2) under a variety of conditions. The degradation was studied by monitoring the change in substrate concentration employing UV spectroscopic analysis technique and depletion in total organic carbon (TOC) content as a function of irradiation time. The degradation kinetics of the model compound was investigated under different conditions such as type of TiO2, pH, catalyst concentration, substrate concentration, temperature, and in the presence of different electron acceptors such as hydrogen peroxide (H2O2), potassium persulfate (K2S2O8), and potassium bromate (KBrO3) besides molecular oxygen. TiO2 Degussa P25 was found to be a more efficient photocatalyst for the degradation of the model compound as compared with other photocatalysts. The degradation products were analyzed using GC/MS analysis technique and probable pathways for the formation of different products have been proposed.     

Belite cement clinker from coal fly ash of high Ca content. Optimization of synthesis parameters

The optimization of parameters of synthesis of belite cement clinker from coal fly ash of high Ca content is presented in this paper. The synthesis process is based on the hydrothermal-calcination-route of the fly ash without extra additions. The hydrothermal treatment was carried out in demineralized water and a 1 M NaOH solution for 4 h at the temperatures of 100 degrees C, 150 degrees C, and 200 degrees C. The precursors obtained during the hydrothermal treatmentwere heated at temperatures of 700 degrees C, 800 degrees C, 900 degrees C, and 1000 degrees C. The changes of fly ash composition after the different treatments were characterized by X-ray diffraction (XRD), FT infrared (FTIR) spectroscopy, surface area (BET-N2), and thermal analyses. From the results obtained we concluded that the optimum temperature of the hydrothermal treatment was 200 degrees C, and the optimum temperature for obtaining the belite cement clinker was 800 degrees C.     

Photodegradation of dye pollutants catalyzed by porous K3PW12O40 under visible irradiation

Microporous solid K3PW12O40 is prepared by precipitation of phosphotungstic acid and potassium ion, followed by calcination. Using this material as photocatalyst, a series of dye pollutants, such as rhodamine B, malachite green, rhodamine 6G, fuchsin basic, and methyl violet, were efficiently degraded in the presence of H202 under visible light irradiation (lambda > 420 nm). The photocatalyst was characterized via SEM, BET surface area, FT-IR, and XRD. The photocatalyst has relative large surface area, and the Keggin structure of phosphotungstic ions is intact during the precipitation and calcination. The degradation kinetics, TOC changes, degradation products, ESR detection of active oxygen species, and the effect of radical scavengers are also investigated to clarify the degradation process and the reaction pathway. The dyes can be facilely bleached and mineralized (ca. 40% of TOC removal for RhB), and the main degradation products of RhB detected, besides CO2, are the small organic acids. They are released from the surface of the catalyst to the bulk solution during the degradation of the dye, which avoids the poisoning of photocatalyst by the intermediates. The formation of active oxygen species such as the O2-*/ HO2* and *OH are detected during the degradation of dye, and they are proposed to be responsible for the degradation of dyes. The K3PW12040 catalyst is very stable and very easily separated from the reaction system for reuse.     

等碳量添加不同有机物料对土壤有机碳组分及土壤呼吸的影响

为探明不同有机物料对土壤有机碳组分和呼吸速率的影响,研究了等碳量添加生物炭、秸秆、生物炭+秸秆条件下烤烟生长过程中土壤总有机碳（TOC）、易氧化有机碳（ROC）、可溶性有机碳（DOC）、微生物量碳（MBC）含量及土壤呼吸速率的动态变化,分析了土壤各有机碳组分之间及其与土壤呼吸速率的关系。研究结果显示,与单施化肥相比,等碳量添加有机物料后土壤各有机碳组分含量以及土壤呼吸速率均显著提高;添加有机物料的3个处理中,单施生物炭处理土壤TOC含量最高,CO₂排放量最低;单施秸秆处理土壤活性有机碳（AOC）占TOC的比例及CO₂排放量最高,但TOC含量最低;生物炭+秸秆处理土壤TOC含量显著高于添加秸秆处理,AOC含量显著高于单施生物炭处理,且CO₂排放量显著低于单施秸秆处理。土壤ROC、DOC、MBC之间关系密切,三者与土壤呼吸速率均呈显著正相关。由此可见,等碳量添加有机物料条件下,生物炭有利于土壤有机碳的固存,可减少CO₂的排放,但短期内对提高土壤AOC的效果不如秸秆直接还田明显,而秸秆直接还田对土壤AOC含量的提升效果最好,但会增加CO₂的排放,两者配施既提高了土壤AOC的含量,又减少了CO₂的排放。      

Estimates of increased black carbon emissions from electrostatic precipitators during powdered activated carbon injection for mercury emissions control

The behavior of mercury sorbents within electrostatic precipitators (ESPs) is not well-understood, despite a decade or more of full-scale testing. Recent laboratory results suggest that powdered activated carbon exhibits somewhat different collection behavior than fly ash in an ESP and particulate filters located at the outlet of ESPs have shown evidence of powdered activated carbon penetration during full-scale tests of sorbent injection for mercury emissions control. The present analysis considers a range of assumed differential ESP collection efficiencies for powdered activated carbon as compared to fly ash. Estimated emission rates of submicrometer powdered activated carbon are compared to estimated emission rates of particulate carbon on submicrometer fly ash, each corresponding to its respective collection efficiency. To the extent that any emitted powdered activated carbon exhibits size and optical characteristics similar to black carbon, such emissions could effectively constitute an increase in black carbon emissions from coal-based stationary power generation. The results reveal that even for the low injection rates associated with chemically impregnated carbons, submicrometer particulate carbon emissions can easily double if the submicrometer fraction of the native fly ash has a low carbon content. Increasing sorbent injection rates, larger collection efficiency differentials as compared to fly ash, and decreasing sorbent particle size all lead to increases in the estimated submicrometer particulate carbon emissions.     

Mechanistic aspects of the de-novo synthesis of PCDD/PCDF on model mixtures and MSWI fly ashes using amorphous 12C- and 13C-labeled carbon

The formation of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) from amorphous 12C- and 13C-labeled carbon was studied on model mixtures and real fly ashes. PCDD/F can either be formed directly (de-novo) from carbon already present in fly ash or step-by-step via condensation of two aromatic rings. Using model mixtures containing 12C- and 13C-labeled carbon in various ratios we observed the formation of the following compound classes: 12C6-PCPh, -PCBz, 13C6-PCPh, -PCBz, 12C12-PCDD/ F, 13C12-PCDD/F, and 12C6 13C6-PCDD/F. By examining the fraction of the mixed PCDD/F (one of the two aromatic ring is composed solely of 12C-atoms while the other contains only 13C-atoms) in the total concentration of PCDD/F, conclusions on the formation of these three ring structures are possible. From the experimental results, it can be concluded that both reaction mechanisms are operative in the formation of PCDD/F from carbon. On fly ashes approximately half of the total amount of PCDD is formed via condensation of de-novo created C6-precursors e.g. chlorophenols, while the remainder is directly released (de-novo) from the carbon i.e., formed from a related C12-structure. However, the condensation of intermediate aromatic C6-precursors is of minor importance in the formation of PCDF. With increasing temperature the relative amount of the 12C6 13C6-PCDD formed by condensation decreases due to the faster evaporation of chlorophenols. At a constant reaction temperature, the ratio of both reaction pathways is hardly influenced by reaction time. In experiments with fly ashes doped with 13C-labeled carbon, this carbon isotope shows a similar reactivity as the native carbon present on the fly ash. Thus, the used amorphous carbons are suitable models for this investigation.     

Partial removal of PCDD/Fs, coplanar PCBS, and PCBS from municipal solid waste incineration fly ash by a column flotation process

Municipal solid waste incineration (MSWI) fly ash has recently attracted much attention because of its large quantity and enrichment of high toxic combustion generating organohalogen contaminants such as polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), coplanar polychlorinated biphenyls (coplanar PCBs), and polychlorinated biphenyls (PCBs). Since the organohalogen contaminants in MSWI fly ash are known to be enriched in the unburnt carbon (UC) fraction, the organohalogen contaminants can therefore be removed by the removal of UC. In this research, we used a modified column flotation technique to remove the organic contaminants from MSWI fly ash. UC was removed for 27.7% under the flotation condition without chemical flotation aids. The removal efficiencies of UC, PCDD/Fs, coplanar PCBs, and PCBs are further improved by adding flotation aids during the flotation process. UC was removed for 49.0% by adding a collector assistant with a HLB value of 13.5 and a concentration in the kerosene of 3% during the flotation process. In addition,the UC removal efficiencies are increased with the decrease of the diameter of the micropores in the gas spargers. By optimizing the flotation condition, 41.9% total PCDD/Fs, 40.8% coplanar PCBs, and 44.1% PCBs with 64.0% UC have been successfully removed from MSWI fly ash. The total toxic equivalent (TEQ) of the fly ash was decreased from 6.2 ng/g to 4.2 ng/g in the residue.     

Reactivity of alkaline lignite fly ashes towards CO2 in water

The reaction kinetics between alkaline lignite fly ashes and CO2 (pCO2 = 0.01--0.03 MPa)were studied in a laboratory CO2 flow-through reactor at 25--75 degrees C. The reaction is characterized by three phases that can be separated according to the predominating buffering systems and the rates of CO2 uptake. Phase I (pH > 12, < 30 min) is characterized by the dissolution of lime, the onset of calcite precipitation and a maximum uptake, the rate of which seems to be limited by dissolution of CO2. Phase II (pH < 10.5, 10--60 min) is dominated by the carbonation reaction. CO2 uptake in phase III (pH < 8.3) is controlled by the dissolution of periclase (MgO) leading to the formation of dissolved magnesium-bicarbonate. Phase I could be significantly extended by increasing the solid-liquid ratios and temperature, respectively. At 75 degrees C the rate of calcite precipitation was doubled leading to the neutralization of approximately 0.23 kg CO2 per kg fly ash within 4.5 h, which corresponds to nearly 90% of the total acid neutralizing capacity.