Dehalogenation Potential of Municipal Waste Incineration Fly Ash

BACKGROUND, AIMS AND SCOPE: In the first part of this paper the main principles which control the dehalogenation of polychlorinated aromatic compounds on municipal waste incineration fly ash (MWI-FA) have been discussed and the model fly ash of similar dehalogenation activity has been proposed. Even if both systems show comparable dehalogenation properties, the main question concerning the postulated identical reaction mechanism in both cases is left unanswered. The other very important point is to what extent is this dechlorination mechanism thermodynamically controlled. The same problem is often discussed in the literature also for the de novo synthetic reactions. From the data it is clear that metallic copper plays a decisive role in the mechanism of the dehalogenation reaction. Although the results reported in the first part strongly support the idea that copper acts in this dechlorination as the reaction component, in contrast to its generally accepted catalytic behaviour, we believed that additional support for this conclusion can be obtained with the help of a thermodynamic interpretation of the mechanism of the reaction. RESULTS AND DISCUSSION: The pathways of hexachlorobenzene dechlorination on MWI-FA and model fly ash were studied in a closed system at 260-300 degrees C under nitrogen atmosphere. These pathways were the same for both systems, with the following prevailing sequences: hexachlorobenzene --> pentachlorobenzene --> 1,2,3,5-tetrachlorobenzene --> 1,3,5-trichlorobenzene --> 1,3-dichlorobenzene. Thermodynamic calculations were carried out by using the method of minimization total Gibbs energy of the whole system. In the calculations, the following reaction components were taken into account: all gaseous chlorinated benzenes, benzene, hydrogen chloride, a gaseous trimer Cu3Cl3, and also Cu2O and CuCl2 as solid components. The effect of the reaction temperature and the amount of copper and water vapour were considered as well. The effect of reaction temperature was determined from the data calculated for the 500 to 750 K temperature region. The effect of the initial composition was determined for the molar amounts of copper = 0.01-3 moles and water vapour = 0.2 to 3 moles per mole of chlorobenzene isomer CONCLUSIONS: The results of hexachlorobenzene dechlorination by MWI-FA and model fly ash under comparable reaction conditions allow us to conclude that both dechlorinations proceed via the same dechlorination pathways, which can be taken as an evidence of the identical dehalogenation mechanism for both systems. The relative percentual distribution of the dehalogenated products depends on the temperature, but not on the initial amount of water vapour or copper metal. On the other hand, the initial amount of copper substantially affects the conversion of the dehalogenation as well as the molar ratio of Cu3Cl3 to HCl in the equilibrium mixture. Comparison of the experimental with thermodynamic results supports the idea that dehalogenation reactions are thermodynamically controlled. RECOMMENDATIONS AND OUTLOOK: Thermodynamic analysis of the dehalogenation reactions may prove useful for a wide range of pollutants. The calculations concerning polychlorinated biphenyls and phenols are under study.     

Effects of selected metal oxides on the dechlorination and destruction of PCDD and PCDF

OCDD and OCDF spiked silica/graphite based model fly ash containing various copper compounds and metal oxides were thermally treated under oxygen deficient conditions. All copper compounds tested showed a considerable dechlorination/hydrogenation reaction at 260 °C. After 30 min at 340 °C, less than 1% of the spiked OCDD and OCDF was recovered as T₄CDD/F to OCDD/F. Other compounds tested demonstrated a lower rate of dechlorination compared to the copper compounds. However, all other metal oxides showed a small dechlorination effect at 260 °C, which was considerably increased at 340 °C.

The model fly ash containing the different copper compounds or metal oxides showed comparable PCDD and PCDF isomer patterns after thermal treatment. However, small differences were observed among the different tested compounds. The PCDD and PCDF isomer patterns on the model fly ashes were similar to patterns found during dechlorination experiments on fly ashes from waste incineration processes.

Model fly ash containing Ca(OH)₂ exhibited the highest destruction potential, but a low dechlorination potential. In contrast, model fly ash containing any of the remaining compounds tested, was found to predominantly dechlorinate the spiked OCDD and OCDF.     

超临界水无害化共处理PVC和医疗垃圾焚烧飞灰的可行性探讨

采用超临界水氧化降解PVC同时无害化处理医疗垃圾焚烧飞灰,利用PVC脱氯形成的中间产物盐酸提取医疗垃圾焚烧飞灰中的重金属,达到飞灰无害化的目的。结果显示,超临界水可以将飞灰颗粒打碎,从而提高盐酸提取重金属的速率和效果,但是在超临界水中还存在重金属的固定过程,过长的反应时间和过高的反应温度都会降低重金属的提取效率。在提取过程中,Cu和Zn优先于Pb被盐酸浸出,而Pb被浸出后很容易被超临界水进一步固定。综合考虑重金属在超临界水中的变化特性,总结出超临界水处理飞灰和PVC的最佳条件为:PVC与飞灰质量比0.5:1,温度400℃,提取时间90 min。处理后的飞灰再次经过水洗后,其重金属浸出浓度低于USEPA规定的限制值。本研究为飞灰的无害化处理提供一条新的思路。     

粉煤灰资源化特性及路面工程应用技术研究

对粉煤灰的各项技术参数进行了试验研究,揭示出粉煤灰的不同成分和形貌对其资源化特性的影响规律,初步完成了消除不利于粉煤灰资源化的有害成分炭的优化实验工作,进行了脱炭粉煤灰混凝土配合比等试验研究,并在路面修复工程中予以应有,结果表明,经脱炭处理的粉煤灰应用于混凝土工程可以明显改善混凝土的工作性能,实际道路运营和技术性能符合路面工程的要求,具有重大的经济效益和环境效益。     

Effect of fly ash characteristics on the removal of Cu(II) from aqueous solution

Fly ash is a particulate substance containing metal oxides, carbon and other microelements. In this study, fly ashes with different quantities of carbon and minerals prepared by a thermal process in the laboratory were used as adsorbents to investigate the contribution of precipitation and adsorption to the removal of aqueous Cu(II). Experimental results showed that the specific surface area of fly ash increased linearly with the quantity of carbon. The specific surface areas of the carbon and mineral fraction were 60 m2/g and 0.68 m2/g, respectively. The specific adsorption capacities of carbon ranged from 2.2 to 2.8 mg Cu/g carbon, while those for mineral were only about 0.63 to approximately 0.81 mg Cu/g mineral. Consequently, the carbon fraction in fly ash was important in the removal of Cu(II) at pH 5. However, Cu(II) removal owing to precipitation increases with a decreasing carbon fraction and the contribution of copper precipitation was estimated to be approximately 23% to approximately 82% of total removal, depending on the carbon fraction of fly ash.     

Dechlorination and destruction of PCDD,PCDF and PCB on selected fly ash from municipal waste incineration

The potential of fly ash to dechlorinate and destroy PCDD, PCDF and PCB was tested under oxygen deficient conditions in the laboratory. Specifically, two types of fly ash were compared, originating either from a fluidized bed incinerator using Ca(OH)₂ spray (FA1), or a stoker incinerator without Ca(OH)₂ impact (FA2).

Results from the present study indicate that on FA2 type fly ash, the degradation processes of OCDD, OCDF and D₁₀CB occurred primarily via dechlorination/hydrogenation up to temperature settings of 340 °C. In contrast, FA1 type fly ash was found to effect both dechlorination and destruction of these compounds already at temperature settings of 260 °C.

The dechlorination velocity of PCDD and PCDF did not differ significantly. However, the first dechlorination step of OCDF in the 1,9-position occurred faster compared to the first dechlorination step of OCDD.

The isomer pattern resulting from the dechlorination processes was quite similar on both FA1 and FA2, indicating that differences in alkalinity or elemental composition of the two types of fly ashes do not have a significant influence on the position of dechlorination. PCDD and PCDF dechlorination of the 2,3,7,8-positions was not favoured over dechlorination of the 1,4,6,9-positions on either type of fly ash. In contrast, dechlorination of PCB occurred predominantly on the toxicological relevant 3- and 4-positions.

The dechlorination/destruction processes were completed on both types of fly ash at 380 °C within one hour, which correlates well with results obtained from actual plant operation practices.     

水泥对垃圾焚烧飞灰的固化处理试验研究

对垃圾焚烧飞灰的化学成分、重金属物质的含量及浸出浓度进行测试分析.结果表明,飞灰中Pb和Cr等重金属物质浸出量超过浸出毒性标准,因而被认为是危险废物,必须进行固化处理.还考察了水泥对焚烧飞灰中重金属物质固化的效果,研究表明当飞灰掺量适当时,重金属物质的固化效果良好.重金属物质通过物理固封、替代,沉淀反应和吸附等形式可固化进水泥水化产物结构中.     

Effect of fly ash on sorption behavior of metribuzin in agricultural soils

This investigation was undertaken to determine the effect of two different fly ashes [Kota and Inderprastha (IP)] amendment on the sorption behavior of metribuzin in three Indian soil types. The IP fly ash was very effective in increasing the metribuzin sorption in the soils. The sorption with IP amendment was increased by 15–92%, whereas with the Kota fly ash an increase in sorption by 13–38% was noted. The adsorption isotherms fitted very well to the Freundlich adsorption equation and, in general, slope (1/n) values less then unity were observed. Although both the fly ashes significantly decreased metribuzin desorption, the IP fly ash was comparatively more effective in retaining metribuzin in the soils. Metribuzin sorption in the IP fly ash-amended soils showed strong correlation with the fly ash content and compared to K_f/K_d values, K_FA values (sorption normalized to fly ash content) showed less variation. Metribuzin sorption-desorption did not correlate to the organic carbon content of the soil-fly ash mixture. The study demonstrates that all coal fly ashes may not be effective in enhancing the sorption of metribuzin in soils to the same extent. However, among the fly ashes used in this study, the IP fly ash was observed to be significantly effective in enhancing the sorption of metribuzin in soils. This may play an important role in reducing the run off and leaching losses of the herbicide by retaining it in the soil.     

EXAFS study of adsorbed Cu(II) on fly ashes with different residual carbon contents.

This work studied the speciation of copper species adsorbed onto the surface of fly ash using X-ray absorption spectroscopy (XAS). Experimental results verified that the chemical bond between Cu(II) and the surface of the fly ash was Cu-O. The data set was optimally fitted into the two atomic shells: the first shell containing O atoms and the second shell containing Cu atoms. The extended X-ray absorption fine structure (EXAFS) data also show that, in the first shell, about 2.03-2.41 nearest oxygen atoms surround the center Cu atom with a Cu-O bond distance of 1.96-1.99 A. The results further demonstrated that the bond distance slightly increased with an increasing carbon content of the fly ash.     

锡冶炼含砷烟尘低温陶瓷固化技术

以锡冶炼过程中排放的含砷烟尘为研究对象,对浸出特性和低温陶瓷胶凝材料对其的固化效果进行了研究。结果表明,含砷烟尘As、Cu和Zn毒性浸出浓度分别为6 783、167和224 mg/L,严重超过国家毒性浸出鉴别标准值。其经低温陶瓷胶凝材料固化处理,当含砷烟尘掺量小于40%,自然养护3 d,As、Cu和Zn毒性浸出浓度急剧降低,且低于国家标准值。XRD和SEM分析表明,低温陶瓷胶凝材料在复合化学激发剂作用下,反应生成类沸石水化铝硅酸盐矿物(Al-O-Si);固化体中Ca-Fe-As-O盐是As固化的主要矿物相。Cu2+、Zn2+替换铝硅酸盐聚合物结构中的Na+、K+保持平衡电荷。胶凝材料水化产物填充于材料颗粒间,使其连接成一致密整体,有效降低了有害物质的毒性浸出浓度。     

CaCl2高温热处理垃圾焚烧飞灰中重金属的挥发特性

以深圳市某垃圾焚烧厂飞灰为原料，采用高温管式电阻炉，研究了在0．6L／minN，气氛下，CaCl2在不同添加量、处理温度及处理时间下对飞灰中重金属Pb、Cd、Zn和Cu挥发特性的影响，并对收集到的二次飞灰进行成分及物相分析。结果显示，X射线衍射仪和EDS分析表明，二次飞灰主要是由NaCl、KCl和部分SiCl4组成，zn主要以K2ZnCl4形式挥发，而Pb则主要以氧化物PbO和Pb3SiO5的形式挥发。最终得到CaCl2热处理飞灰的最佳二次气化条件：以0．6L／minN，为载气，添加14wt％的CaCl2，在1100℃高温下处理2．5h。经CaCl2热处理后的剩余飞灰，其浸出毒性达到了《生活垃圾填埋场污染控制标准》要求。     

SGA对垃圾焚烧飞灰中重金属的固化性能研究简

根据EPA 1311、HJ/T 299-2007、HJ/T 300-2007和HJ 557-2009等国内外不同标准，研究了深圳某垃圾焚烧发电厂垃圾焚烧飞灰的浸出毒性，探讨了六硫代胍基甲酸（sixthio guanidine acid，SGA）、二甲基二硫代氨基甲酸盐（sodium dimethyl dithio carbamate，SDD）和Ca（OH）₂浓度对垃圾焚烧飞灰中重金属的固定性能的影响。研究结果表明，随着浸提液pH的降低，该厂焚烧飞灰中大部分金属元素的浸出量增大，焚烧飞灰浸出液中的Cd、Ni、Pb和Zn浓度分别超过国家危险废物鉴别标准（GB5085.3-2007）规定值的4.75倍、1.47倍、6.72倍和2.20倍，属于危险废弃物，必须进行稳定化处理。当固化剂SGA加入量为0.1 mol/kg时，稳定化后的重金属浸出浓度已经低于危险废物鉴别标准，且对Cd、Cr、Cu和Pb的固化性能优于SDD和Ca（OH）₂；当固化剂SGA、SDD和Ca（OH）₂加入量为0.5 mol/kg时，稳定化后的焚烧飞灰重金属浸出浓度均低于国家危险废物鉴别标准（GB 5085.3-2007）中的规定值。与SDD和Ca（OH）₂相比，SGA对垃圾焚烧飞灰中重金属的固化处理更具有优势。     

壳聚糖联合碱改性粉煤灰对重金属离子的吸附特性

采用浸渍法将壳聚糖负载在经NaOH改性的粉煤灰上，制备了联合改性的粉煤灰。随粉煤灰上壳聚糖负载量的增加，粉煤灰对Pb²⁺和Cd²⁺的吸附率均提高。当负载壳聚糖的质量分数为8%，吸附温度为30℃，吸附时间为120 min时，粉煤灰对Pb²⁺的吸附率最高（为98.9%），对Cd²⁺的吸附率也最高（为91.5%）。其吸附行为符合Freundlich等温吸附模型，但表现为2个线性区。粉煤灰负载壳聚糖的改性机理是粉煤灰与带正电荷的壳聚糖的化学键合作用。     

Reduced downward mobility of metribuzin in fly ash-amended soils

Metribuzin, a triazine herbicide, is poorly sorbed in the soils, therefore leaches to lower soil profile. Fly ash amendment, which enhanced metribuzin sorption in soils, may play a significant role in reducing the downward mobility of herbicide. Therefore, the present study reports the effect of Inderprastha fly ash amendment on metribuzin leaching in three soil types. Fly ash was amended at 1, 2 and 5% levels in the upper 15 cm of 30 cm long packed soil columns. Results suggested a significant reduction in the leaching losses of metribuzin in fly ash-amended columns of all the three soil types and effect increased with increase in the level of fly ash. Even after percolating water equivalent to 362 mm rainfall no metribuzin was recovered in the leachate of 5% fly ash-amended columns. Fly ash application affected both metribuzin breakthrough time and its maximum concentration in the leachate. Further, it resulted in greater retention of metribuzin in the application zone and better effect was observed in the organic carbon poor soils.     

火力发电厂飞灰对抗生素磺胺的吸附性能

研究了吸附时间、飞灰用量、初始溶液pH和振荡频率等因素对飞灰吸附去除水溶液中磺胺的影响,并对其吸附机理进行了初步探讨。研究结果表明,飞灰用量增大有利于提高其对磺胺的吸附去除率。在25℃、振荡频率150 r/min、飞灰用量50 g/L、磺胺浓度4 mg/L条件下吸附10 min,磺胺的吸附去除率可达到92.8%。电厂飞灰对磺胺的吸附符合二级动力学模型,属于单分子层吸附。     

铁屑粉煤灰组合处理含磷废水

实验研究了铁屑粉煤灰组合处理含磷废水的除磷效果.通过单因素实验,考查了铁屑粉煤灰质量比、反应时间、pH值和投加量对除磷效果的影响.实验结果表明,该法除磷的最优条件为铁屑和粉煤灰的质量比为2∶1,反应时间为20 min,pH值为6,投加量为20 g/L.在最优实验条件下磷的去除率达到了97.5％.对比了该法和粉煤灰吸附法与传统铁屑法的除磷效果.与单一粉煤灰吸附法和传统铁屑法除磷的结果相比较,铁屑粉煤灰组合除磷的方法具有明显优势.     

粉煤灰资源化的现状

本文检索了国内外综合利用粉煤灰的有关文献 ,由粉煤灰特性入手 ,介绍了它在农业、建筑、环保等行业的资源化现状。指出粉煤灰作为二次资源的重要意义 ,并对粉煤灰资源化提出了一些设想     

Dechlorination ability of municipal waste incineration fly ash for polychlorinated phenols

Pathways of pentachlorophenol dechlorination have been investigated on municipal waste incineration fly ash at 200 degrees C under nitrogen atmosphere. Thermodynamic calculations have been carried out for these dechlorination conditions using the method of total Gibbs energy minimization for the whole system consisting of gaseous components, i.e., chlorinated phenols, phenol, hydrogen chloride and the Cu3Cl3 trimer and of solid Cu2O and CuCl2 components. The effects of water, temperature and of the amounts of the reaction components on the thermodynamic equilibrium have been discussed and the experimental results compared with the calculated thermodynamic data.     

Low-temperature dechlorination of hexachlorobenzene on solid supports and the pathway hypothesis

The dechlorination of HCB was carried out under low-temperature and oxygen deficient conditions on different solid supports such as SiO(2), CaO, CaSiO(3), cement and treated fly ash (tFA). All the tested supports except SiO(2) showed a HCB dechlorination potential. The dechlorination efficiencies (D(1)) of HCB by CaO, CaSiO(3), tFA and cement reached 64.62%, 76.15%, 79.97% and 32.21% at 350 degrees C for 4h, respectively. It was thought electrons in the vacancies originated from the unsaturated metallic ions and O(2-) on the crystal surfaces made the D(1) different between SiO(2), CaO and CaSiO(3). Comparing the D(1) by tFA and cement, the high dechlorination potential of tFA was due to the more free electrons from the crystal defects and the transition metals, and the more active points for the gas-solid phase reaction, which both had positive effects on dechlorination reaction. The effect of Cu addition (0.2-5.0%) on HCB dechlorination might result from the Ullmann coupling which was not notable in enhancing the dechlorination reaction. From the study, we can draw the conclusion that the dechlorination potential mainly depends on the support characteristic rather than the transition metal content. Based on this study and previous references, the dechlorination/polymerization induced by the electron transfer mode was thought to be the dominant pathway while the hydrogen transfer mode was minor. The electron was originated from the crystal defects or induced by transition metals, and the dissociation of a chloride ion happened forming a radical, and then the polymerization of radicals led to the formation of high-molecular-weight compounds which seemed to cause the material imbalance.     

回收粉煤灰磁珠在污水处理中的应用

从粉煤灰综合利用角度,探时利用回收粉煤灰中磁珠作磁种,用高梯度磁分离技术进行污水处理的可行性,进一步研究了粉煤灰磁珠粒度组成对污水处理效果的影响。