Effect of pH on the flotation performance of incinerator fly ash

Flotation was proved to be effective for decarburization and removal of dioxins from hospital solid waste (HSW) incinerator fly ash, but weathering makes it difficult. The effects of three types of surfactants including nonionic (Tween 80), anionic (SDS), and cationic (CTAB) at different pulp pH values on the flotation performance of weathered HSW incinerator fly ash were investigated. Results showed that the corresponding optimal pH values of Tween 80, CTAB, and SDS were 7, 5, and 9 in terms of decarburization performance, respectively, which were validated by the measurement of Zeta potential. The total dioxins and carbon removal efficiencies showed good correlation at various pulp pH values with surfactant of Tween 80. The optimum surfactant type and pH value should be selected as Tween 80 and pH = 7 from the standpoints of the dioxin removal. Under the optimum condition, the lowest content of dioxins (2.7 ng I-TEQ/g) in the tailings was obtained. The content of heavy metals in the froths exhibited higher with addition of SDS compared with that with Tween 80 and CTAB.     

Effect of flotation on the dioxin distribution in size-fractioned fly ash of hospital solid waste incineration

After the flotation of hospital solid waste incinerator (HSWI) fly ash, two types of solid products, froths and tailings, are produced. This paper reports the effect of flotation on the dioxins distribution patterns in different particle size fractions (?25, ?38, +25, ?75, +38, ?106, +75 and +106 µm) of fly ash. The results showed that the froths had a higher small-size particle distribution than that of the raw fly ash. The dioxin content with particle size in the flotation products depended on the partition behavior of powder-activated carbon (PAC). The dioxin content in the fine particles of the froths was higher than that in the coarse particles, and the highest content was in the finest particles (?25 µm). The dominant dibenzo-p-dioxins and dibenzofurans (PCDD/F) congeners in the froths and tailings were similar to those in the raw fly ash. A positive correlation between carbon removal and PCDD/F removal with different size fractions was observed. The carbon removal efficiencies of the fractions of ?25 and ?38, +25 µm were evidently higher than those of the other particle size fractions. Similarly, the PCDD/F removal efficiencies in fractions of ?25 and ?38, +25 µm could reach 156.9% and 115.0%, respectively.     

Degradation of PCDD/Fs in MSWI fly ash using a microwave-assisted hydrothermal process

In this work, microwave treatment was introduced to a hydrothermal treatment process to degrade PCDD/Fs (Polychlorinated dibenzo-p-dioxins and dibenzofurans) in municipal solid waste incineration (MSWI) fly ash. Three process additives (NaOH, Na₂HPO₄, H₂O), temperatures (150℃, 185℃, 220℃) and reaction times (1 h, 2 h, 3 h) were investigated to identify their effect on the disposal of fly ash samples through orthogonal experiments. High-resolution gas chromatography-mass spectrometry (HRGC/MS) was applied to determine the PCDD/F concentrations in MSWI fly ash. The experimental results revealed that 83.7% of total PCDD/Fs was degraded. Reaction temperature was the most important factor for the degradation of the total PCDD/Fs. Both direct destruction and chlorination reactions (the chlorination degree of PCDFs increased) took part in the degradation of PCDD/Fs in fly ash, which was a new discovery. Several PCDD/F indexes determined by the concentration of indicative congeners were found to quantitatively characterize the dioxin toxicity of the fly ash. Furthermore, heavy metals in the fly ash sample were solidified using microwave-assisted hydrothermal treatment, which provided an experimental basis for the simultaneous disposal of dioxins and heavy metals. Thus, the microwave-assisted hydrothermal process should be considered for the future disposal of MSWI fly ash.     

Removal of heavy metals from municipal solid waste incineration (MSWI) fly ash by traditional and microwave acid extraction

BACKGROUND: Municipal solid waste incinerator (MSWI) fly ash is regarded as hazardous waste because it contains various toxic metals. A previous study has shown that fly ash can be detoxified by removal of heavy metals. In this work, the extractability of heavy metals from MSWI fly ash by traditional and microwave acid extraction were compared. RESULTS: A 2^{4 ? 1} fractional factorial experimental design was adopted using acid concentration, extraction time, temperature, and liquid/solid (L/S) ratio as the experimental factors for traditional extraction, and acid concentration, extraction time, liquid/solid (L/S) ratio and microwave power as the experimental factors for microwave extraction. The traditional extraction results show that L/S played an important role in Zn, Cd extraction while L/S ratio and extractant concentration were important for Pb extraction. However, no controlling parameter was determined for Cu and Cr extraction. For the microwave extraction, it was shown that L/S was important for Pb and Zn and extractant concentration was important for Pb, Zn and Cd. The time and the power were not significant for the extractability of heavy metals. CONCLUSION: Hydrochloric acid was an effective extractant. Microwave heating promoted extraction and shortened extraction time. Microwave acid extraction treatment is a potentially feasible method for the removal of heavy metals from MSWI fly ash. Copyright © 2010 Society of Chemical Industry     

垃圾焚烧飞灰熔融过程二(口恶)英分解特性

引　言焚烧处理技术凭借其高效快捷和显著的减量效果在城市固体废弃物 (MSW )处理领域日益占有重要地位 .随着社会的进步和公众环保意识的逐渐提高 ,焚烧过程的二次污染尤其是二英的排放成为限制焚烧处理推广的瓶颈问题[1,2 ] .目前我国的垃圾焚烧过程排放二英限值为 1 0ng     

Detoxification of medical waste incinerator fly ash through successive flotation

Medical waste incinerator (MWI) fly ash is considered hazardous waste because it contains hypertoxic polychlorinated dibenzo-p-dioxins and dibenzofurans as well as heavy metals. To detoxify both substances, successive flotations of MWI fly ash were performed. The first step involved decarburization flotation, whereby 91.0% of the dioxins in MWI fly ash were transformed into a froth product. In the second step (ion flotation), the influence of ionic strength on heavy metals recovered from both raw and stimulated filtrates was explored. The results revealed that the optimal conditions were sodium dodecyl sulfate at 480 ppm, methyl isobutyl carbonyl at 150 ppm, impeller speed at 2000 rpm, and flotation time of 18 min for raw leachate, through which Zn (47.0%), Pb (56.5%), Cu (57.5%), and Cd (49.1%) were recovered. For the simulated filtrate, higher removal efficiencies were noted: 60.5%, 80.6%, 69.1%, and 64.1% for Zn, Pb, Cu, and Cd, respectively. The harmful effects of the coexisting ions in the raw filtrate on heavy metal recovery were observed.     

电渗析法分离医疗垃圾焚烧飞灰浸出液中重金属

采用电渗析法分离医疗垃圾焚烧飞灰浸出液中重金属,考察了电流密度、液固比、处理时间等参数对重金属移除的影响,并分析了电渗析处理对飞灰特性、重金属形态及其浸出毒性的影响. 结果表明,电流密度0.8 mA/cm2、液固比10(w)和处理时间14 d条件下飞灰浸出液中重金属分离效果最好,11.1% Pb, 42.3% Zn, 56.7% Cd, 38.7% Cu, 7.5% Cr被移除,飞灰中大量NaCl被移除,氯含量从20.43%降低到0.78%,热灼减率从11.1%升高到34.3%,可溶态和碳酸盐态重金属含量降低,飞灰基质减少及不可溶态重金属存在导致残灰中重金属含量增加,Pb和Cd浸出浓度仍超过生活垃圾填埋场的阈值.     

固体废物焚烧灰渣毒性评估及其控制方法研究进展

固体废物焚烧产生的灰渣时环境是一种二次污染物,其中,焚烧飞灰因其含有重金属及有毒有机污染物而被列为危险固体废物,因此在其最终处置前,必须进行稳定化处理.作者介绍了灰渣的污染特性,尤其是飞灰中所含重金属、有毒有机污染物的毒性及其各种评估方法,包括水平震荡法、浸出柱实验法、毒性浸出程序(TCLP),并综述了当前灰渣的控制技术方法和资源化利用手段,如水泥固化法、熔融固化法、化学药剂固化法.     

硫酸铵和尿素抑制飞灰合成二(口恶)英

二(口恶)英(PCDD/Fs)排放制约了当前焚烧技术在垃圾处置和资源化利用领域的应用和推广。研究了硫酸铵和尿素在不同温度下对垃圾焚烧飞灰合成PCDD/Fs的抑制能力。实验结果表明:高温下(650℃)硫酸铵和尿素对PCDD/Fs合成具有更高的抑制效率,但高温下飞灰合成PCDD/Fs量远低于低温下(350℃)的生成量;PCDD/Fs的降低量均主要来自于PCDFs的减少,并且低温下TeCDF减少量最大,而高温下减少最多的同系物为OCDF。由于实际烟道中,高温处投入的抑制剂会进入低温段继续产生抑制作用,所以仍需要更多的研究正确评价抑制剂的抑制效果和最优使用温度。     

上海城市生活垃圾焚烧飞灰的性质分析

垃圾焚烧飞灰是我国城市垃圾焚烧新技术发展过程中产生的一个新问题,飞灰中有大量有害物质。必须予以安全处置。而飞灰的性质对如何处置以及处置的效果非常重要。飞灰的性质有很大的地域性差异。我们对上海浦东御桥垃圾焚烧厂产生的飞灰的相关性质如化学组成、重金属浸出率、重金属挥发特性等进行了检测。并对结果进行了分析。结果表明：上海市飞灰中SiO2含量较高。有利于进行熔融固化。但飞灰在熔融过程中。重金属的挥发量较大,需要引起注意。     

Vitrification of municipal solid waste incineration fly ash: An approach to find the successful batch compositions

Incineration is the most common way to reduce the mass and the volume of municipal solid wastes. One of the most dangerous by-products of the incineration process is fly ash that contains a considerable amount of heavy metals. Therefore, its treatment is crucial to prevent the leaching of heavy metals into the environment. In the present work, two different sources of municipal solid waste incinerator fly ash have been vitrified in order to inhibit the release of potentially toxic heavy metals. Two different sources of silica, i.e. silica sand and glass cullet, have been added to each type of fly ash in an attempt to obtain vitrifiable batches. The standard leaching test on vitrified products was performed according to EN12457-2 confirming no heavy metal leaching and, therefore, they all pass waste acceptance criteria to be classified as an inert material. Furthermore, the previously reported data for vitrification of fly ash was combined with the present work and their compositions were presented in the SiO₂–Al₂O₃–CaO, and SiO₂-ΣM₂O₃-Σ(MO + M₂O) ternary phase diagrams to identify the region in which successful compositions are concentrated. This analysis could facilitate the attempt to find the right composition for vitrification of fly ash.     

医疗废物焚烧炉启炉过程二噁英排放特性

选择了位于华东地区的某医疗废物焚烧处置设施开展启炉过程与正常工况下烟气和飞灰的二噁英排放特性对比研究。数据显示, 启炉后期烟气中二噁英的浓度达到1.68 ng I-TEQ·m^-3, 在焚烧炉温度稳定以后12 h, 达到2.77 ng I-TEQ·m^-3, 飞灰中二噁英毒性当量水平也达到4.5 ng I-TEQ·g^-1。启炉过程中烟气中气相二噁英所占比例逐渐增加, 从平均占到50%增加到超过90%。启炉过程中烟气二噁英排放速率高于其正常达标时的排放水平, 最高值为58.1 mg I-TEQ·h^-1, 超过正常排放的40倍。一个启炉周期二噁英的排放总量达到0.785 mg I-TEQ, 达标正常工况下二噁英的年排放总量为8.4 mg I-TEQ, 按照平均每年3次启炉来计算, 启炉过程二噁英的排放量占到全年正常排放的28%。     

Behavior of heavy metals in air pollution control devices of 2,400 kg/h municipal solid waste incinerator

We analyzed the behavior of heavy metals, such as Cd, Cr, Cu, Ni, Pb, Zn, and Hg, in air pollution control devices of a municipal solid waste incinerator. For this study, a municipal solid waste incinerator with a burning capacity of 2,400 kg/h was selected. A semi-dry reactor (SDR), fabric filter, and wet scrubber were installed to serve as air pollution control devices. Flue gas was sampled upstream and downstream of each air pollution control device to determine the heavy metal concentrations therein. Ash was collected from the furnace, boiler, SDR, and fabric filter to determine the heavy metal concentration in the ash produced by each device. Each heavy metal was found to have a different fate in the incinerator and air pollution control devices. Cd and Pb were mostly present in the fabric filter ash, whereas Cr, Cu, and Ni were most prevalent in the bottom ash of the furnace and boiler, and Zn was present in the bottom and fabric filter ash at a ratio of 7: 3. However, only a few percent of Hg was identified in the ash from the furnace, boiler, SDR, and fabric filter; the majority of Hg passed through the fabric filter and existed in an oxidized form. The wet scrubber exhibited high control efficiency for oxidized mercury, and the injection of commercial activated carbon at a rate of 0.2 g/Sm³ resulted in 93.2% mercury removal efficiency.     

五氯酚在飞灰表面低温反应生成二口恶英特性

在管式炉上研究了不同试验条件飞灰/五氯酚生成二口恶英的分布特性.采用色质联机(HRGC/LRMS)测定了PCP中以及生成产物中的二口恶英含量.结果表明，生成产物中的二口恶英主要以气态形式存在，总的二口恶英中以PCDDs为主，比例高于97％，PCDDs中主要同系物是六至八氯代PCDDs.分析了飞灰含量以及氧含量对二口恶英生成的影响，二口恶英生成量随着飞灰中含碳量的增加而增大，氧含量是控制二口恶英生成的关键因素，氧含量在6.7％时生成的二口恶英总量及毒性当量值最小.对试验中产生的二口恶英进行了质量平衡，为进一步研究垃圾焚烧过程中二口恶英排放以及分布特性打下基础.     

垃圾焚烧飞灰水洗脱氯及重金属浸出特性研究

系统研究了机械炉排炉垃圾焚烧飞灰水洗过程中氯化物和重金属的浸出特性,并采用Visual MINTEQ模拟分析水洗液中重金属的存在形态。结果表明：飞灰中的氯主要以可溶性氯化钠（NaCl）、氯化钾（KCl）、氯化钙（CaCl₂）、碱式氯化钙（CaClOH）的形式存在,飞灰水洗浸出成分97%以上为氯离子（Cl^-）、钠（Na）、钾（K）、钙（Ca）,其中氯离子占比高达60%;重金属及其他成分的浸出量很少,不足1%。水洗对氯离子的去除效果非常明显,可达92%以上,但是重金属的浸出量极低。飞灰单次水洗最佳条件：液固体积质量比为6 mL/g,洗涤时间为10 min。Visual MINTEQ模型分析表明,pH是控制飞灰水洗液中铅（Pb）、铜（Cu）、锌（Zn）、镉（Cd）形态的重要因素,氯离子（Cl^-）对镉的形态分布也有着重要的影响。飞灰水洗液电导率与氯离子质量浓度具有极好的线性相关性,其可作为监测滤液中氯离子质量浓度变化的有效间接指标。     

SO2抑制二英从头合成的实验及其过程模拟

实验研究了不同温度下SO₂对二 英（PCDD/Fs）从头合成的抑制特点,运用HSC Chemistry 6.1软件对主要无机化学反应过程进行模拟,探究了SO₂的抑制机理。结果表明,SO₂对PCDD/Fs总浓度和I-TEQ浓度的抑制效果随温度的升高而增强。PCDD/Fs总浓度和I-TEQ浓度抑制率从200℃不足20%分别提高到300℃时的75.6%和77.3%及400℃时的89.2%和80.5%;SO₂的添加促进了PCDD/Fs尤其是PCDDs同系物分布的低氯代化。在从头合成的高温段和低温段,SO₂分别侧重抑制PCDFs和PCDDs。相平衡计算和Gibbs自由能计算表明,SO₂优先与催化剂CuCl₂反应生成无催化活性的CuSO₄,其次与氯源Cl₂反应,最终实现PCDD/Fs的生成抑制。模拟结果对现有硫基抑制机理进行了验证和补充,对高效、廉价抑制剂的开发及工程使用具有重要意义。     

城市生活垃圾焚烧飞灰组成特性及重金属熔融固化处理技术研究进展

近年来,我国城市生活垃圾清运量以每年5%左右的增速发展,垃圾焚烧处理能力不断提升,而垃圾焚烧过程会产生占焚烧总量3%~5%的垃圾焚烧飞灰。随着垃圾焚烧处理能力的不断提升,垃圾飞灰产量逐年增加,飞灰处置压力越来越大。城市生活垃圾焚烧飞灰作为一种高重金属浸出毒性的危险废弃物,对环境存在较大危害。论述了城市生活垃圾焚烧飞灰的组成特性及重金属的分布和性质,从飞灰熔融过程原理、重金属转化特性、重金属固化影响因素等方面阐述了熔融处理垃圾飞灰技术的研究进展,探究了飞灰组分和熔融条件对熔融过程及重金属固化效果的影响。论述了等离子熔融技术和熔融固化重金属的效果,最后对飞灰复配熔融及冷却过程优化处理给出参考性建议,并指出飞灰熔融处理技术未来发展方向。垃圾焚烧飞灰中重金属主要以其氧化物、氯化物、硫酸盐形式存在,熔融处理可以改变飞灰组分及相态,使飞灰发生多晶转变和熔融相变过程,重金属离子发生同晶置换反应,被固化在硅酸盐的Si—O四面体晶格结构中,很大程度上降低了飞灰的浸出毒性并实现熔渣资源化利用。熔融处理过程中,熔融气氛、时间及飞灰组分对过程特性和重金属的迁移转化影响较大,冷却方式不同会影响玻璃体熔渣的物理性质。根据重金属的熔点和沸点特性,在熔融处理后,烟气和二次飞灰中会携带部分挥发性强、沸点低的重金属。在今后研究中需要对烟气和二次飞灰进行冷却或二次捕集处理,并对烟气成分进行探究。由于熔融处理过程耗能大、投资高、关键设备研发难攻关,我国垃圾焚烧飞灰熔融处理技术仍处于技术研发阶段,尚无稳定化工业运行实例,但已有部分中试研究试验。熔融处理前,应先分析飞灰组成成分,根据飞灰组成进行预处理。通过添加助熔剂、调节飞灰碱度对飞灰进行复配熔融处理,降低熔融处理的能耗,高效稳定处理重金属。在实验室稳定有效试验的基础上,可以对等离子体熔融处理装置进行技术改进和创新,提高等离子火焰稳定性,实现熔渣的高效分离,提升装置耐久性。     

Electrodialytic extraction of Cu,Pb and Cl from municipal solid waste incineration fly ash suspended in water

The possibility of using fly ash from municipal solid waste incineration (MSWI) in, for example, concrete is considered. MSWI fly ash, however, has too high a concentration of heavy metals, which may cause leaching problems during use or problems with waste handling at the end of the lifetime of the concrete. The Cl content in MSWI fly ash is also too high and will cause corrosion problems in reinforced concrete. The possibility of removing some of the unwanted heavy metals (Cu and Pb) together with Cl from an MSWI fly ash suspended in water using an electrodialytic separation method was investigated. The removal of Pb and Cu was found to be highly pH dependent and the highest contents removed were 41 and 90%, respectively. The Cu concentration of the ash decreased from 2200 to 860 mg kg^?1 but the Pb concentration increased from 8560 to 16 800 mg kg^?1, showing that Pb is mainly found in the ash fraction that is least soluble. Hence electrodialytic treatment of the ash suspended in water is not a solution to improve the ash quality in terms of Pb. The water‐soluble Cl content per unit weight of the original ash was 12.4%. The removal of water‐soluble Cl was efficient and >98% of Cl was removed (calculated on the basis of mean initial and final concentrations). This result indicates that electrodialytic extraction may be a method that can be used for the removal of Cl from ash prior to its utilization in concrete. Copyright © 2006 Society of Chemical Industry     

粉煤灰作为廉价吸附剂控制污染物排放的研究进展

能源转化过程中煤炭燃烧产生大量粉煤灰,如何通过减少其对生态环境造成的负担和提高其经济效益实现粉煤灰资源化利用,已成为了国内外研究的热点。本文综述了煤粉在高温燃烧过程中经过物理和化学变化形成粉煤灰的原理,分析了粉煤灰组成、结构和形貌,阐述了其主要利用途径。重点介绍了粉煤灰作为廉价吸附剂,在脱除烟气中SOx、NOx、Hg、有机气体、CO2以及脱除废水中重金属离子、P和F及有机化合物（如酚类、农药、染料、石油烃类有机污染物）等应用。许多研究证实粉煤灰中未燃烧的炭在吸附污染物过程中起到重要作用,通过物理和化学处理改性后可明显提高粉煤灰的吸附性能。粉煤灰在烟气和废水污染物控制方面应用前景良好,利用粉煤灰制备分子筛进行污染物处理将是今后粉煤灰发展的重要方向。     

不同底物浓度下生物淋滤垃圾焚烧飞灰中重金属的动力学研究

通过氧化硫硫杆菌生物淋滤处理城市垃圾焚烧飞灰中的重金属。采用分批摇床培养,研究了生物淋滤过程中,底物浓度(S)对飞灰中重金属去除速率的影响。采用经验方程研究了S浓度对飞灰中重金属去除速率的影响,得到不同S浓度下4种重金属(Cu、Zn、Cd、Pb)的去除速率常数km,其大小顺序为ZnCuCdPb。综合各个动力学参数推知S浓度为5 g/L是本生物淋滤体系的最佳底物浓度。