城市生活垃圾焚烧过程中二次污染物的生成与控制

在我国，采用焚烧法处理城市固体垃圾，逐渐得到推广和应用，然而焚烧带来的二次污染物，如二恶Ying，细颗粒，重金属，HCl以及SOx,NOx等也随之引起了广泛关注，对垃圾焚烧过程中各种二次污染物的产生机理及其控制方法进行了综述。并且指出近期我国城市固体垃圾焚烧烟气污染物的重点控制对象应为颗粒物，HCl,SOx和NOx。     

城市生活垃圾焚烧过程中二次污染物的生成与控制

在我国 ,采用焚烧法处理城市固体垃圾 ,逐渐得到推广和应用。然而焚烧带来的二次污染物 ,如二、细颗粒、重金属、HCl以及SOx、NOx 等也随之引起了广泛关注。对垃圾焚烧过程中各种二次污染物的产生机理及其控制方法进行了综述。并且指出近期我国城市固体垃圾焚烧烟气污染物的重点控制对象应为颗粒物、HCl、SOx 和NOx。     

流化床垃圾焚烧炉产生的有毒二(口恶)英同类物分布研究

测定了流化床垃圾焚烧炉焚烧产生的飞灰、烟尘和烟气中的2,3,7,8位氯取代二(口恶)英同类物的含量及其毒性当量.结果表明,产生的二(口恶)英主要存在于飞灰中,烟气中的含量很少.飞灰中二(口恶)英总浓度和毒性当量分别为8.44ng/g和0.80ng/g,经过布袋除尘器后的烟尘和烟气中二(口恶)英的浓度之和与毒性当量之和分别为0.34 ng/m3和0.02 ng/m3,而布袋除尘器前的烟尘和烟气中二(口恶)英的浓度之和与毒性当量之和分别为40.78 ng/m3和3.01ng/m3.飞灰和烟尘中2,3,7,8位氯取代二(口恶)英同类物的分布相似,但是与烟气中2,3,7,8位氯取代二(口恶)英同类物的分布差别较大.通过了解有毒二(口恶)英同类物的分布,可以进一步优化流化床垃圾焚烧炉的焚烧条件,降低二(口恶)英的排放量,减少垃圾焚烧对环境的污染.     

垃圾焚烧飞灰中的重金属污染物处理方法

随着垃圾焚烧技术在各个城市生活垃圾处理中的广泛应用,对生活垃圾焚烧的残余物,主要是飞灰的处理、处置,已成为困扰人们生产生活的重要难题之一。飞灰的处理是控制重金属污染的关键,目前处理垃圾焚烧飞灰中重金属污染物的常用方法有：水泥固化法、化学药剂稳定法、飞灰热处理、化学浸提法等,生物淋滤法是近年新兴起来的金属浸提技术。经处理后的飞灰可进行填埋或资源化利用。因此,着重叙述了当前有关垃圾焚烧飞灰中重金属污染的控制方法与处置技术的研究现状。     

熔盐法处置高熔点垃圾焚烧飞灰重金属的浸出特性

对熔盐法处置高熔点垃圾焚烧飞灰重金属离子浸出特性进行了实验研究。结果表明,熔盐物料组成、熔盐温度和热处理气氛对重金属离子的热挥发特性具有重要影响。在还原性气氛条件下,热处理温度为900~1 000℃,添加质量分数为10%~50%的CaCl_2的氯化钠熔盐中处理2 h后,垃圾焚烧飞灰渣中Pb、Cd、Cu和Zn等重金属浸出浓度降低90%以上,可以完全达到生活垃圾填埋场填埋标准。在此过程中,灰渣较原灰可减轻50%,同时转化成具有良好胶凝性能的水泥活性混合材料,XRD测试表明其晶体矿物组成为硅酸二钙、硅酸三钙和阿里尼特以及硫酸钙等。     

销毁含多氯联苯废弃物焚烧炉的二噁、类二噁和多氯联苯排放

我国正在研制专用于销毁高浓度多氯联苯（ＰＣＢｓ）的焚烧炉,主要处理废旧的含（ＰＣＢｓ）的电力电容器和变压器,应用可靠准确的监测方法测定了试验性焚烧炉渣、烟灰排气和废水中的二口恶口英（ｄｉｏｘｉｎｓ）,类二口恶口英多氯联苯（ｄｉｏｘｉｎｌｉｋｅＰＣＢｓ）和ＰＣＢｓ含量,结果表明该炉试烧高浓度ＰＣＢｓ时,焚毁率可以达到９９．９９９９％,炉渣中的２,３,７,８ＴＣＤＤ毒性当量为８７．８６ｐｇＴＥＱ／ｇ,烟灰中残留二口恶口英和类二口恶口英的总２,３,７,８ＴＣＤＤ毒性当量为４７．２３ｎｇＴＥＱ／ｇ．     

垃圾焚烧飞灰中重金属固化稳定机理及系统评价方法的研究进展

垃圾焚烧飞灰中的重金属是必须处理的环境污染物.目前,对于垃圾焚烧飞灰的固化稳定化处理已经有了大量的实验研究.但是,不同地区垃圾焚烧厂产生的飞灰中,重金属含量和形态大不相同,故相应的飞灰仍然难以实现大规模、普适性的处理.在查阅文献及实际调研的基础上,系统总结了垃圾焚烧飞灰中重金属的存在形态与浸出特性;通过对重金属固化稳定...     

垃圾焚烧飞灰综合利用研究进展

焚烧处理是解决日益增长生活垃圾的有效方法。垃圾焚烧产生的飞灰因含有大量的重金属等污染物而属危险废物，目前常采用的处理方法是填埋。本文就垃圾飞灰的综合利用研究现状进行了论述。从环境和技术的角度看，垃圾飞灰的预处理、水泥固化和玻璃化是目前飞灰综合利用的主要研究方向。     

150t／d循环流化床生活垃圾焚烧炉的工艺结构与污染排放

垃圾焚烧处理技术在我国的应用越来越广泛，单纯引进国外的垃圾焚烧处理技术已经无法满足我国经济发展的需要。清华大学自主开发研制的150t／d循环流化床生活垃圾焚烧炉已经通过专家鉴定，各项焚烧污染物徘放指标均达到或优于国家标准，总体水平居国内领先水平。本文详细介绍了该焚烧炉的系统及结构，并对有关控制污染物排放的技术手段进行了详细分析。     

大气中二（口/恶）（口/英）研究进展

二（口/恶）（口/英）是世界公认的强致癌物质,对人体健康危害极大.近年来,大气中二（口/恶）（口/英）的研究已成为各国环境化学家研究的热点.本文总结了近年来国际上有关大气中二（口/恶）（口/英）研究的进展情况,以及所取得的主要研究成果,并在此基础上指出了我国目前研究中存在的问题及以后所应开展的工作.     

Formation of dioxins (PCDDs/PCDFs) by dioxin-free fly ash as a catalyst and relation with several chlorine-sources

Simplified thermal formation experiments have been conducted using dioxin-free fly ash as a catalyst with many kinds of combustible samples such as newspaper, kerosene, paraffin, PE (polyethylene), PP (polypropylene) and PVC. Chlorine sources were PVC, NaCl and HCl. The combustion of samples containing chlorine in the absence of dioxin-free fly ash produced dioxins at a low level although HCl was present in the gas stream. On the other hand, the combustion of samples without chlorine with dioxin-free fly ash increased dioxins formation to a level around 10 times higher than that upon heating dioxin-free fly ash alone. This result is considered to be due to the presence of metal chloride in the fly ash and hydrocarbons in the gas stream. The combustion of samples containing either an organic or inorganic chlorine source or using a HCl stream with dioxin-free fly ash increased dioxin level dramatically.     

The effects of temperature and oxygen content on the PCDD/PCDFs formation in MSW fly ash

In this study, the effects of the temperature, oxygen content in the gas stream and carbon content in ash particles on PCDD/Fs formation on the fly ash surface were investigated. The optimum temperatures for dioxin formation were found at 350 degrees C for boiler ash, 300 degrees C for cyclone ash and 250 degrees C for ESP ash, respectively. Preliminary results indicate that the optimum temperature will decrease as the particle size decreases. When the O2 concentration is varied between 0% and 100%, the optimum oxygen content for PCDD/Fs formation is found to be at 7.5% for cyclone ash, and the PCDD/PCDF ratio increases with the increase of oxygen content. Dioxin formation is observed even for the gas containing no oxygen passed through the fly ash. Hence, other reacted routes that do not need O2 for dioxin formation take place on fly ash. The carbon content in fly ash is varied between 0% and 20% in this study, and the results have indicated that the maximum dioxin formation is to be found at 5%. The precursors are not injected into the fly ash or gas stream in all formation experiments, however, dioxin is still formed in fly ash. Consequently, other chlorinated routes besides Deacon reactions may take place on the fly ash surface.     

The Relationship between the Quantity of Heavy Metal and PAHs in Fly Ash

ABSTRACT

Heavy metal and polycyclic aromatic hydrocarbons (PAHs) in flue gas have received considerable attention in recent years due to their mutagenic or carcinogenic properties. The present study is carried out to investigate the influence of the quantity of heavy metals on PAHs formation in fly ash.

A fluidized bed incinerator was used in this experiment to obtain fly ash of chemical similarity by incinerating various compositions of waste. The obtained fly ash, both with and without heavy metal, were used to adsorb the PAHs in the flue gas and to investigate the formation of PAHs in fly ash. The results indicate that carbon and heavy metals most greatly influence the formation of PAHs in the fly ash. Carbon is absorptive; heavy metals encourage not only absorption of PAHs but also catalyze PAHs formation.     

Solubility analysis and disposal options of combustion residues from plants grown on contaminated mining area

Biomass, as a renewable energy source, is an excellent alternative for the partial replacement of fossil fuels in thermal and electric energy production. A new fuel type as biomass for energy utilisation includes ligneous plants with considerable heavy metal content. The combustion process must be controlled during the firing of significant quantities of contaminated biomass grown on brownfield lands. By implementing these measures, air pollution and further soil contamination caused by the disposal of the solid burning residue, the ash, can be prevented. For the test samples from ligneous plants grown on heavy metal-contaminated fields, an ore mine (already closed for 25 years) was chosen. With our focus on the determination of the heavy metal content, we have examined the composition of the soil, the biomass and the combustion by-products (ash, fly ash). Our results confirm that ash resulting from the combustion must be treated as toxic waste and its deposition must take place on hazardous waste disposal sites. Biomass of these characteristics can be burnt in special combustion facility that was equipped with means for the disposal of solid burning residues as well as air pollutants.     

De novo formation characteristics of dioxins in the dry zone of an iron ore sintering bed

The objectives of this work are to understand the details of the mechanism of dioxin formation in the part of a sintering bed termed the dry zone, and to obtain ideas on how to prevent their formation. Sinter mixtures of various composition types were heated in a packed bed reactor, and dioxins in the outlet gas and in the sinter mixture residue were measured. The dioxin formation potential of a simple sinter mixture composed of iron ore, coke and limestone was markedly lower than that of fly ash from a municipal solid waste incinerator (MSWI). In consideration of this result, a series of experiments were conducted using a sinter mixture impregnated with CuCl2. Experimental results showed that dioxin formation was temperature-dependent in the range of 300-550 degrees C, with the maximum observed at around 300 degrees C, which was quite similar to that of fly ash from the MSWI. The homologue distribution of PCDD/Fs in gas and solid reflected the possible difference in carbonaceous materials in coke and activated coke. Gaseous hydrogen chloride acted as a chlorinating reagent for dioxin formation.     

可渗透反应复合电极法对土壤重金属的电动去除

将零价铁(Fe0)、沸石等活性材料附着在电极上形成可渗透反应层并构成可渗透反应复合电极,采用不同的复合电极对Cd2+、Ni 2+、Pb2+和Cu2+等4种阳离子型重金属污染土壤进行了电动力学修复。研究了不同可渗透反应复合电极对土壤pH的控制效果以及对重金属的去除作用,分析了迁移到复合电极中的重金属形态变化。结果表明,复合电极中添加酸、碱性沸石并适时更换,可有效中和、截留阴阳极电解产生的OH-和H+,避免或减缓土壤酸碱迁移带的形成,防止重金属离子的过早沉淀及土壤过度酸化,极大提高了重金属的去除率。复合电极中Fe0可将迁移进来的重金属离子进行还原稳定,实现重金属污染物的捕获与固定,与迁移到沸石复合电极中的4种重金属不稳定态相比,"Fe0+沸石"复合电极中重金属不稳定态分别下降了61.4、60.5、61.4、57.1百分点。结果还显示,阴极采用"Fe0+沸石"复合电极并适时进行更换,施加1.5V/cm的直流电压修复10d后,土壤中Cd、Ni、Pb、Cu的总去除率分别为44.5%、41.5%、33.5%和36.7%,且进一步延长修复时间和持续更换电极可获得更为理想的修复效果。     

危险废物回转式流化冷渣多段焚烧系统焚烧特性研究

危险废物的处理和处置是摆在我国各级市政府面前的紧迫任务。然而我国已经运行的危险废物焚烧装置普遍存在回转窑挂壁结渣、热灼减率偏高和污染排放超标等问题,作者通过将回转窑和流化床特点相结合的方法提出了一种新型危险废物回转式流化冷渣多段焚烧处置装置。该装置采用回转窑(一燃室)、二燃室和流化床结合的热解-流化焚烧工艺,特别是采用控制窑头温度避免了回转窑挂壁结渣;采用流化冷渣装置延长未燃烬渣的焚烧时间,解决了热灼减率偏高问题;水冷式烟气急冷装置可以将烟气温度从1 100℃降到200℃,防止了二恶英的尾部低温再生成。该系统运行稳定可靠,可以处理医疗垃圾和大多数的固态和液态危险废物,实现了烟气污染物尤其是二恶英排放达到国家标准的目标。同时对该系统运行时窑头温度分布、二燃室炉膛出口氧量变化、回转窑和炉膛升温特性、燃烧室外壁温度分布等几方面运行数据都进行了详细的介绍,为危险废物焚烧炉的运行提供了宝贵的经验数据。     

Heavy metal solubility in podzolic soils exposed to the alkalizing effect of air pollutants

The heavy metal content of pine forest soil was studied near the boundary between Russia and Estonia, an area characterized by large amounts of acidic and basic air pollutants, mainly sulfur dioxide and calcium. Alkalization dominates the processes in soil, since sulfur is adsorbed only in small quantities, and calcium is much better adsorbed. In addition to Ca, great amounts of Al, Fe, K, and Mg are accumulated in the humus layer due to air pollution. The heavy metal content has increased. The exchangeable content of heavy metals was in many cases much higher in polluted alkaline soils than in non-polluted acidic soils, even the ratio of exchangeable to total metal content being higher in alkaline plots. To avoid a dangerous increase in soluble heavy metal content, it is important to decrease not only the large sulfur emissions of local pollutant sources, but also the alkaline pollutants. A similar concern must be taken into account when liming of acidic forest soils is planned.     

Changes in Chlorinated Organic Pollutants and Heavy Metal Content of Sediments during Pyrolysis (7 pp)

Background There has been an increasing concern about the treatment and disposal of contaminated sediment from dredged river, harbor or estuary due to the accumulated toxic organics such as dioxins and inorganics particularly heavy metals like Cr, Pb, Zn, Cu, Hg and Cd. However, considering the huge amount of materials and financial costs involved, any candidate technology must ultimately result to reusable residual by-products. This can only be made possible if the toxic pollutants are removed or stabilized in the raw sediment and then fed back into the materials cycle. Currently, we are developing a pyrolysis process for the commercial-scale cleanup of dioxins and heavy metal-contaminated river sediment to yield reusable char for various economical applications. In this connection, this paper describes our preliminary investigation into the extent of dioxins and heavy metal volatilization from actual contaminated sediment. The stabilization of certain metallic species particularly Cr ions was studied. Methods Laboratory scale pyrolysis experiments were conducted using a special horizontal lab-scale pyrolyzer. Sediment samples from Shanghai Suzhou Creek and Tagonoura Harbor were pyrolyzed in the reactor under nitrogen gas at 800°C and different retention times of 30, 60 and 90 min. A constant heating rate of 10°C min-1 was employed. The pyrolysis gas was first allowed to pass through a cold trap to condense the tar. Uncondensed gases were then channeled through a column containing an adsorbent (XAD-2 Resin) for dioxins. Heavy metal concentrations in the initial and final sediment residues were analyzed by ICP (Nippon Jarrel-Ash) following their acid and alkali (for Cr6+) digestion. Dioxins content of the pyrolysis char, tar, and exhaust gases in the dioxin adsorbent were also determined. For comparative purpose, thermal treatment under air flow was conducted. Results The data for the removal of heavy metals from Suzhou Creek sediment showed very significant reductions in Pb, Zn and Cr6+ content of the sediment at this condition. Percentage removals were 42.4%, 60.8% and 42.2%, respectively. The disappearance of Cr6+ was due to reduction reactions rather than volatilization since the total Cr content remained almost unchanged. Other heavy metals such as Cu, Fe and Ni showed very minimal reductions. Nonetheless, Toxicity Characteristics Leaching Procedure (TCLP) tests confirmed that these residual heavy metals were rather stable in the pyrolysis char. Reduction of toxic Cr6+ at 42.2% has also been achieved by pyrolysis (with N2) as opposed to the more than 580 % increase in Cr6+ observed during thermal oxidation (with air). Discussion Pyrolysis also remove toxic organics particularly dioxins from the sediment. For the total dioxins, removal percentage of 99.9999% was achieved even at the lowest retention time of 30 min. Almost all polychlorinated dibenzo-p-dioxine (PCDDs) and polychlorinated dibenzo-furans (PCDFs) were removed at any retention time. The TEQs detected from the solid residues were mainly contributed by dioxin-like PCBs, yet these were present in relatively trace quantities. At the shortest retention time of 30 min, only 0.000085 pg-TEQ g-1 of polychlorinated biphenyls (PCBs) was detected in the pyrolysis char. Furthermore, the residual PCBs have very low toxicity ratings and none of the highly toxic PCBs, which were initially present in the sediment such as 3,3',4,4',5-PeCB and 3,3',4,4'5,5'-HxCB, were detected in the char. Results further confirmed that most of the dioxins that were removed were transferred to the gas phase so that volatilization may be considered as the main mechanism for their removal. Conclusion Some heavy metals particularly Pb and Zn can be volatilized under N2 pyrolysis at 800oC. Pyrolysis also prevented the formation of more toxic Cr6+ ions and at the same time resulted to its reduction by around 42.2% contrast to the 580% increase during thermal oxidation. PCDDs and PCDFs have been removed and were not formed in the solid products over the retention time range of 30-90 min at 800°C. Dioxin-like PCBs mostly remained and a retention time of 30 min was found sufficient for its maximum removal. Recommendations and Perspective . With the above results, a temperature of 800oC at a retention time of 30 min is sufficient for the removal of total dioxins and some heavy metals by volatilization. It is however necessary to destroy the dioxins as well as recover heavy metals in the gas phase. Stability of remaining heavy metals in the char also needs to be confirmed by leaching tests. These are the major concerns, which we are currently evaluating to establish the feasibility of our proposed large scale pyrolysis system for sediment treatment.