医疗垃圾焚烧飞灰重金属形态分析

利用原子吸收光谱仪分别对医疗垃圾焚烧飞灰重金属含量和重金属形态及其随颗粒度分布特性进行了分析,结果表明,飞灰中Cd、Zn、Pb等的浸出浓度远超标与这些重金属的可交换态和碳酸盐态含量较高有关;飞灰颗粒度主要在96 μm以下,96～150 μm的颗粒中Cd、Pb含量最高,且Zn、Cd的形态以可交换态为主.     

不同粒度飞灰中16种微量元素的含量分布

研究了不同粒级的燃煤飞灰中的Ｂａ、Ｂｅ、Ｃｄ、Ｃｒ、Ｃｕ、Ｈｇ、Ｌｉ、Ｍｎ、Ｎｉ、Ｐｂ、Ｓｒ、Ｔｉ、Ｖ、Ｚｎ、Ｚｒ元素的含量分布,煤中元素的含量比及富集因子。     

垃圾焚烧飞灰水泥固化体的抗压强度和浸出性研究

利用垃圾焚烧飞灰掺入普通硅酸盐水泥制备水泥固化体,通过浸出性实验,研究了飞灰掺量(0%、20%、40%与60%)、浸出液pH及水洗预处理对水泥固化体抗压强度及重金属(Zn、Pb、Cu、Cd、Cr、Ni)浸出的影响。结果表明:对于非水洗飞灰水泥固化体,pH为4.2和10.0下浸出84 d时,相同组成固化体抗压强度较为接近,飞灰掺量20%,40%和60%的固化体抗压强度分别为41、15和10 MPa左右;除掺量为40%和60%的固化体浸出液中重金属(pH为4.2时Ni和Pb,pH为10.0时Ni)超出生活饮用水卫生标准(GB 5749-2006)外,掺量为40%和60%的固化体的其余浸出液及掺量20%的固化体浸出液中测定的重金属浓度均符合生活饮用水卫生标准。对于水洗飞灰水泥固化体,pH为4.2和10.0下浸出84 d时,相同组成固化体抗压强度较为接近,飞灰掺量20%、40%和60%的固化体抗压强度分别为37、32和10 MPa左右;除掺量为60%的固化体浸出液(pH为4.2和10.0)中Ni和Pb均超出生活饮用水卫生标准外,掺量为60%的固化体的其余浸出液及飞灰掺量20%和40%的固化体浸出液中测定的重金属浓度均符合生活饮用水卫生标准。飞灰水洗预处理提高了飞灰掺量40%水泥固化体抗压强度,同时降低了重金属浸出性。     

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.     

垃圾焚烧飞灰的资源化处置前景

对大量数据进行统计分析,得出垃圾焚烧飞灰中主要重金属元素和二噁英类物质的含量分布特征,并根据垃圾焚烧飞灰的综合特点,结合其他领域现有技术,初步提出了3个垃圾焚烧飞灰的资源化处置方案:①烧制陶粒;②作为凝石成岩剂的原料;③作为上流式厌氧污泥床(UASB)或膨胀式颗粒污泥床(EGSB)废水处理装置的生化反应促进剂.同时回收重金属,并对其前景进行了初步分析.若将上述3个方案逐步完善,不但能节约1000～2000元/t的垃圾焚烧飞灰处置费用,还能够产生很大的附加经济效益.     

流化床飞灰固化焚烧飞灰效果及微观分析

以深圳某垃圾焚烧厂焚烧飞灰为例分析了焚烧飞灰的性质和重金属毒性.结果表明,飞灰中 Pb 和 Cr 超出TCLP 阈值,必须进行稳定化处理.以流化床飞灰为主要成分配制固化材料,按不同比例掺人焚烧l￡灰进行固化实验,结果表明,实验范围内重金属固定效果良好.微观测试显示,固化过程主要产物有水化硅酸钙凝胶、钙矾石等,通过物理包胶、物理吸附、复分解沉淀反应和同晶替代等作用抑制重金属浸出.     

Differential pulmonary inflammation and in vitro cytotoxicity of size-fractionated fly ash particles from pulverized coal combustion

Exposure to airborne particulate matter (PM) has been associated with adverse health effects in humans. Pulmonary inflammatory responses were examined in CD1 mice after intratracheal instillation of 25 or 100 microg of ultrafine (< 0.2 microm), fine (< 2.5 microm), and coarse (> 2.5 microm) coal fly ash from a combusted Montana subbituminous coal, and of fine and coarse fractions from a combusted western Kentucky bituminous coal. After 18 hr, the lungs were lavaged and the bronchoalveolar fluid was assessed for cellular influx, biochemical markers, and pro-inflammatory cytokines. The responses were compared with saline and endotoxin as negative and positive controls, respectively. On an equal-mass basis, the ultrafine particles from combusted Montana coal induced a higher degree of neutrophil inflammation and cytokine levels than did the fine or coarse PM. The western Kentucky fine PM caused a moderate degree of inflammation and protein levels in bronchoalveolar fluid that were higher than the Montana fine PM. Coarse PM did not produce any significant effects. In vitro experiments with rat alveolar macrophages showed that of the particles tested, only the Montana ultrafine displayed significant cytotoxicity. It is concluded that fly ash toxicity is inversely related with particle size and is associated with increased sulfur and trace element content.     

The leachability of carbon-14-labelled 3,4-benzopyrene from coal ash into aqueous systems

The leachability of polycyclic aromatic hydrocarbons from coal ash into aqueous systems was studied. Carbon-14-labeled 3,4-Benzopyrene (BaP) was deposited on coal fly ash by adsorption from the liquid phase in quantities of about 10 μg/g ash. After a thermal treatment in air at 120 °C for 2 hours the desorption of BaP was measured using aqueous solutions of acetone and methanol as extractants and liquid scintillation counting as detection method. In all cases the ¹⁴C-recovery was incomplete. Using water as extractant, ¹⁴C-recoveries of about 1 % were found. In the presence of a non-ionic surface active agent (Tween 80) the ¹⁴C-recovery was enhanced significantly. For these reasons further experiments under realistic waste disposal conditions are necessary.     

Dioxins not detected in effluents from coal/refuse combustion

No 2, 3, 7, 8-tetrachlorodibenzo-p-dioxin was detected in effluents from a power plant burning coal supplemented with processed municipal wastes. These negative findings, in contrast with the many reports of the presence of dioxins from waste incineration, are proposed to be due to the high temperature of 1200°C for the combustion of small pieces of refuse with adequate oxygen for times sufficient to insure complete oxidation.     

燃煤过程中微量元素砷和硒形态转化的热力学平衡模拟

砷和硒是煤中的易挥发有毒微量元素。由于砷和硒在燃煤烟气中的浓度极低以及实验条件的限制 ,目前化学热力学平衡分析已成为预报烟气中砷和硒等有毒元素形态分布的主要理论分析方法。本文综述了热力学平衡分析方法应用于砷和硒在燃煤过程中形态转化和平衡分布等方面的研究进展。首先用于热力学平衡分析的是只含有砷或硒一种微量元素和煤中主量元素及氯元素的简单体系 ,并假设烟气中只有理想气体组成的气相和纯凝聚相的理想模型。然而是否考虑砷和硒与其他微量、主量或次量元素的相互作用 ,砷和硒所有可能存在的反应 ,以及在熔融相砷和硒与熔融物的结合会严重地影响模型的预报结果 ,因此 ,目前热力学平衡体系已发展成为含有包括砷和硒在内的多个微量元素和煤中所有主量、次量元素 ,以及包括熔融相在内的非理想多相复杂体系     

Release of mercury vapor from coal combustion ash

The long-term stability of Hg in coal combustion by-products (CCBs) was evaluated at ambient and near-ambient temperatures. Six CCB samples with atypically high levels of total Hg were selected for study assuming a greater potential for release of measurable amounts of Hg vapor. The samples selected included two fly ash samples from U.S. eastern bituminous coal, two fly ash samples from South African low-rank coal, one fly ash from Powder River Basin (PRB) subbituminous coal blended with petroleum coke, and one PRB subbituminous coal fly ash incorporated with flue gas desulfurization material. Air scrubbed of Hg was passed through compacted 100-g aliquots of each sample at 1 mL/min and vented to a gold-coated quartz trap to collect released Hg vapor. The samples were maintained at ambient and near-ambient (37 degrees C) temperatures. All samples released low-picogram levels of Hg after 90 days. No pattern was evident to link the total Hg content to the rate of release of Hg vapor. An average of 0.030 pg Hg/g CCB/day was released from the samples, which equates to 2.2 x 10(-8) lb Hg/ton CCB/year. If this were applied to a coal-fired power plant production of 200,000 tons of fly ash per year, there would be a maximum potential release of 0.0044 lb, or 2.00 g, of Hg per year. Experiments are continuing to determine long-term vapor release of Hg from CCBs. All samples have been set up in duplicate at ambient temperature with an improved apparatus to reevaluate results reported in this article.     

The role of ammonia on mercury leaching from coal fly ash

The Federal Clean Air Interstate Rule issued in March 2005 will result in many power plants employing ammonia-based technologies to control NO(x) emission. The Clean Air Mercury Rule, issued at the same time, will encourage many power plants to use various technologies to remove mercury from flue gas, generating fly ashes that contain elevated concentrations of mercury. Ammonia forms relatively strong complexes with mercury compared to most other cationic elements and, therefore, may change the leaching characteristics of mercury. Understanding the impact of ammonia on the leaching of mercury from fly ash is critical in predicting the potential environmental impact of future fly ash. Batch methods were used to investigate the ammonia impact on mercury leaching from fly ash under different pH conditions. The results indicated that mercury leaching without external ammonia addition is not significant. However, ammonia addition increased mercury leaching in the alkaline pH range, due to the formation of less adsorbable mercury-ammonia complexes. Washed ash released more mercury than the raw ash if the ammonia concentration is the same, mainly due to the dissolution of some ash components during washing which exposed more mercury on ash surface. Mercury adsorption data indicated that more than 90% of available mercury was adsorbed by fly ash even in the presence of 1000 mg l(-1) ammonia addition.     

危险废物焚烧飞灰中重金属的稳定化处理

以上海市某危险废物焚烧厂飞灰为研究对象,采用Na2S、FeSO4、Na3PO4、和Na3C3N3S34种不同类型化学稳定药剂对飞灰进行了稳定化处理,并应用XRD、IR、SEM和连续化学提取法等仪器和手段对Na3C3N3S3处理焚烧飞灰的产物进行分析研究。研究结果表明,Na3C3N3S3对飞灰中的重金属Cr、Pb、Zn的稳定效果最好,Na3PO4对Cr无明显稳定效果。稳定后产物表面变得致密化,Na3C3N3S3与重金属离子生成的沉淀物干燥后无明显晶型存在。经稳定处理后飞灰中的重金属形态由弱酸提取态转化为可氧化态,减少了飞灰中重金属的浸出毒性。     

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     

Synthesis of high-purity Na-A and Na-X zeolite from coal fly ash

Coal fly ash (CFA) was used as a raw material for the synthesis of zeolite molecular sieve. The synthesis began with the pretreatment of CFA to remove impurities (e.g., Fe₂O₃, CaO, etc.) under various acid types (HCl, H₂SO₄, and HNO₃) and acid/CFA ratios (5–25 mL_acid/g_CFA). High product purity (up to 97%) was achieved with HCl (20%wt), and acid/CFA ratio of 20 mL_HCl/g_CFA. The treated CFA was then converted to zeolite by the fusion reaction under various Si/Al molar ratios (0.54–1.84). Zeolite type A was synthesized when the Si/Al molar ratios were lower than 1, whereas sodium aluminum silicate hydrate was formed when the Si/Al molar ratio were higher than 1. The highest water adsorption performance of the zeolite product, i.e., the outlet ethanol concentration of 99.9%wt and the specific adsorption capacity of 2.31 × 10^?2 g_water/g_zeolite, was observed with the Si/Al molar ratio of 0.82. The zeolite was tested for its water adsorption capacity repeatedly 10 times without deactivation.

Implications: This work evaluated the technical feasibility in the conversion of CFA to zeolite, which would help reduce the quantity of waste needed to be landfilled. This adds value to the unwanted material by converting it into something that can be further used. The synthesized products were shown to be quite stable as water adsorbent for the dehydration of ethanol solution.     

Determination of trace rare earth elements in coal fly ash and atmospheric particulates by electrothermal vaporization inductively coupled plasma mass spectrometry with slurry sampling

A method of fluorination assisted electrothermal vaporization (FETV)-ICP-MS with polytetrafluoroethylene as fluorinating reagent was developed for the direct determination of trace rare earth elements (REEs) in coal fly ash and atmospheric particulates. Under the optimal conditions, the detection limits for REEs were 0.1 pg m(-3)(Eu) to 6.7 pg m(-3)(Nd) with the precisions of 4.1%(Yb) to 10%(La) (c=1 microg L(-1), n=9). The proposed method was applied to determine trace REEs in coal fly ash, airborne particulates and NIES SRM No. 8 Vehicle Exhaust Particulates. It was found that the determined values for Y, La, Pr and Nd obtained by slurry sampling FETV-ICP-MS with external calibration coincided with that obtained by pneumatic nebulization (PN)-ICP-MS and slurry sampling FETV-ICP-MS with standard addition. However, the determined values for Ce and Sm obtained by slurry sampling FETV-ICP-MS with external calibration were lower than that obtained by PN-ICP-MS and slurry sampling FETV-ICP-MS with standard addition.     

城市垃圾焚烧飞灰重金属药剂配伍稳定化实验研究

以飞灰中富含的Pb和Zn为目标重金属,对飞灰中重金属药剂配伍稳定化效果了实验研究.选用EDTA、Na2S、NaH2PO4等稳定化药剂和pH值控制,首先将试剂单独投加飞灰中测定重金属浸出浓度,分析各试剂的稳定化效果;然后通过系列试验观察现象,确定试剂最优投加顺序;最后,按照试剂性质制定4个配伍方案,按照最优投加顺序投加试剂,测定分析各个配伍方案的稳定化效果.结果表明:pH值保持在弱碱性(10左右),重金属稳定化效果较好.EDTA二钠、NaH2PO4和Na2S重金属稳定化效果明显,而有机试剂EDTA二钠稳定化效果明显优于NaH2PO4和Na2S;稳定化药剂投加顺序以Na2S、EDTA二钠、NaH2PO4顺序投加处理效果为最佳;配伍方案4处理效果明显优于其他方案,可以实现稳定化药剂配伍相合,提高飞灰中重金属稳定化效果,同时减少有机螯合剂的使用量,从而降低处理成本.     

Influence of coexisting surface-active agents on leachability of dioxins in raw and treated fly ash from an MSW incinerator

The leaching behavior of dioxins from raw and treated fly ash (FA) under the coexistence of several types of surface-active agents (SAAs) was examined by batch leaching tests to obtain significant information not only for evaluating leachability of dioxins as hydrophobic organic pollutants (HOPs) under the severe environment in which SAAs coexist, but also for evaluating the reduction efficiency of dioxin-leachability from the treated FA. Enhancement of dioxin-leachability by sufficient addition of SAAs was observed in the leaching test, whereas addition of a smaller quantity depressed the leachability. The higher the degree of chlorination in PCDDs/PCDFs homologues, the more effectively the SAAs enhanced the leachability. Moreover, there was a large difference in the potential for leachability enhancement due to each surface activity, based on critical micelle concentration (CMC) of the SAAs although Aldrich humic acid enhanced the leachability at a much lower concentration than CMC. A comparison of the leachability in FA treated by several methods showed a difference in the reduction efficiency of leachability, depending on the adsorption of SAAs by each treated FA.     

烧结活化-酸浸法浸出粉煤灰中铝元素

为实现粉煤灰的高效资源化,并控制资源化过程中的能耗,采用NaOH为烧结助剂,利用烧结活化-酸浸法浸出粉煤灰中的铝元素;在探究最佳工艺条件的同时,通过分析烧结产物矿物组成及官能团的变化来探究粉煤灰烧结活化的机理。结果表明,当烧结温度为550 °C、NaOH/CFA 质量比=1.40、硫酸浓度为30%、烧结时间为10 min的条件下,铝元素浸出率可达95.00%以上。在粉煤灰烧结活化过程中,莫来石及非晶态硅铝化合物与NaOH反应,其中的铝氧八面体结构转变为铝氧四面体结构,铝氧四面体与硅氧四面体结构相结合形成以四元环和六元环为基本结构的铝硅酸盐,即八面沸石和霞石。在酸浸过程中,八面沸石和霞石与硫酸发生反应使铝元素以离子形式存在于酸浸液中,其中霞石相更有利于烧结产物的酸浸过程。该研究结果可为烧结活化-酸浸法浸出粉煤灰中铝元素提供参考。