燃煤电厂异相凝并飞灰重金属淋滤特性

采集了燃煤电厂的异相凝并后飞灰，分析了其物理化学特性。并通过淋滤实验研究了飞灰中重金属As、Se、Pb的环境稳定性。结果表明，凝并飞灰的粒径峰值为138.04 μm，而粉煤灰为60.26 μm；凝并后细颗粒凝聚成了较大的颗粒；凝并飞灰中重金属As、Se、Pb含量均高于同工况下粉煤灰中的含量，且后序脱硫环节所产生石膏中重金属的含量有所下降；批淋滤实验研究结果表明，凝并飞灰中的重金属浸出能力受淋滤液的pH值影响较大，温和环境和碱性条件抑制了As的浸出，酸性和碱性条件抑制了Se的浸出，而碱性条件抑制了Pb的浸出。柱淋滤实验研究结果表明，在酸性溶液和水溶液中，凝并飞灰的重金属浸出能力均受到了抑制。     

固体添加剂对垃圾掺烧污泥焚烧飞灰高温过程中重金属挥发特性的影响

在研究垃圾与污泥掺烧后焚烧飞灰中重金属浸出特征的基础上,重点研究了飞灰在1 000 ℃条件下高温处置过程中重金属(Cu、Zn 、Pb、Cd)随不同停留时间的挥发特性及添加剂(CaO、Al₂O₃、SiO₂、高岭土、粉煤灰)对重金属转化与挥发特性的影响。研究结果表明,飞灰中重金属Zn、Pb、Mn含量较高,Ni的含量较低,而毒性较大的Cd达到29.4 mg/kg。浸出液中七种金属都满足危险废物鉴别标准(GB5085.3-1996),并且重金属的浸出浓度受浸取时间及浸取液pH值影响较大。在同样的高温处置条件下,焚烧飞灰中不同重金属的挥发特性有较大的差别。其中,Pb表现出易挥发的特性,其挥发率超过80%,而Cu挥发性较小,其挥发率小于30%。综合来看,飞灰中重金属的挥发性大小依次为Pb>Cd>Zn>Cu。飞灰中添加Al₂O₃和高岭土可以抑制Cd的挥发,添加Al₂O₃后Pb的挥发率有所减少,添加SiO₂、CaO、高岭土、粉煤灰均使Zn的挥发率降低,而对Cu的挥发率没有抑制作用,这与飞灰中高Cl含量及各痕量元素化合物对固体添加剂活性位选择性的竞争吸附有关。     

石嘴山电厂煤中微量元素的迁移释放行为

应用电感耦合等离子体质谱（ICP-MS）和原子荧光光谱（AFS）对中国西北部石嘴山电厂的原煤、底灰和飞灰中Hg、As、Se、Pb、Cr、Cd、Mo、Ni、Co、U和Th 11种微量元素的含量进行了测定。根据底灰和飞灰的产率, 结合微量元素在底灰和飞灰中的含量计算了电厂燃煤过程中微量元素的挥发性。结果表明, Hg、Cd、Se、As四种元素在燃煤过程的挥发率均在50%以上, 最高可达70%。通过对底灰和飞灰在酸性介质下的柱淋滤实验研究了底灰和飞灰中微量元素在60h内的迁移释放行为。Mn、Ni、Co、As四种元素的最大淋出率均超过2.0%, 最高接近10.0%, 并且还未达到淋滤平衡。根据微量元素的挥发和淋滤释放特性建立了电厂煤中有害微量元素在燃烧和淋滤过程中的释放分配模型。结果显示, 燃煤过程中的挥发是微量元素释放的主要形式, 部分元素的淋滤释放也可对周围水环境造成污染。
     

煤中有害元素的洗选洁净潜势

基于8个洗煤厂实采煤样的测试分析以及2个煤样的模拟洗选实验，对煤炭洗选过程中灰分、硫分及20种有害微量元素的脱除率进行了研究，并系统地探讨了这些有害元素的洁净潜势。结果表明：物理洗选不但能降低煤中的灰分与硫分，还能不同程度地脱除煤中有害微量元素；预测在物理洗选过程中，多数煤中灰分以及有害微量元素As、Co、Cu、Cr、Hg与Mn的脱除率大于50％，硫分的脱除率大于30％，其它有害微量元素Ba、Be、Cd、Cl、Mo、Ni、P、Pb、Sb、Se、Th、U、V与Zn的脱除率相对较低或表现出一个宽的变化范围。     

煤中15种微量元素在燃烧产物中的分配

建立了燃煤中１５种向量元素在悄灰和底灰中含量分布的经验公式，该公式可以估算煤中微量元素在燃烧产物中的分配及传输通量。煤中非挥发性元素大部分存在于底灰和飞灰中，挥发性元素进入大气的量较高。     

The leachability of elements in solid wastes

Landfills and waste disposal sites are now routinely used for disposal of solid wastes and their incinerator ashes. Trace elements from these ashes are leached by rain and acid rain into nearby waterways providing a pathway for toxic elements to re-enter the food chain and the human life cycle. This paper examines the mechanism and the extent of leaching of 20 elements viz. Ag, Al, As, Ba, Br, Ca, Cd, Co, Cr, Fe, Hg, La, Sb, Sc, Ce, Sm, Ta, V, W and Zn. Instrumental neutron activation analysis (INAA) was used for the assay. The solid wastes studied are municipal refuse incinerator ash, coal fly ash, hospital incinerator ash, raw sewage sludge and its incinerator ash.     

Coal bioprocessing research at the institute of gas technology

Coal bioprocessing research at the Institute of Gas Technology (IGT) has included solubilization, gasification, desulfurization, denitrogenation, production of specialty chemicals, and the remediation of organic and inorganic wastes associated with coal utilization. Currently, research is focused on desulfurization and remediation. Desulfurization research concerns the development of processes to remove organic sulfur or to convert a portion of pyritic sulfur to sulfuric acid rapidly, thereby serving as a pretreatment to aid the thermochemical conversion of coal to coke and liquid products. The removal of as much as 91% organic sulfur from coal has been achieved, and biodesulfurization of coal has been confirmed by seven analytical techniques performed in six different laboratories. Recent studies have involved the use of molecular genetics to develop strains of bacteria with higher levels of desulfurization activity, and the development of methods for the preparation, storage, and utilization of biodesulfurization catalysts. Remediation studies include the development ofin situ and on-site technologies to treat soil contaminated with coal tar, the leaching of metals from fly ash, and the treatment of waste water resulting from fly ash leaching or from acidic mine drainage (AMD). IGT currently has two projects in EPA’s SITE program concerned with the remediation of coal tar-contaminated soil, and other related technologies are being developed. Efficient laboratory-scale processes for the removal of metals from fly ash and from soil so that the solids pass EPA’s TCLP test, and the subsequent treatment of the leachates or AMD to meet all regulatory requirements have been developed. Data obtained in these projects are presented in particular, and a general discussion of the application of biotechnology to coal is offered.     

Influence of several experimental parameters on As and Se leaching from coal fly ash samples

Coal fly ash leaching process for As and Se is studied. Environmental parameters such as pH, temperature, solid-liquid ratio, particle size and leaching time are taken into account in order to simulate As and Se leaching process for disposal coal fly ash. Analysis of reference materials was carried out by using of hydride generation coupled to atomic fluorescence spectrometry. Plackett-Burman experimental design is used to know the significative parameters, and Box-Behnken experimental design is used to refine the results obtained for these significative parameters. pH and temperature shown a hardly influence in leaching process. Furthermore, leaching time was also significative. According our results, it may be assumed that percentage of As and Se leaching in experimental conditions tested is relatively low for acidic fly ashes.     

The potential of downscaled dynamic column extraction for fast and reliable assessment of natural weathering effects of municipal solid waste incineration bottom ashes

There is a current worldwide interest for evaluating the potential reuse of municipal solid waste incineration (MSWI) bottom ash as a sub-base in road construction and secondary building material. Yet, there is a need for exploration of the physicochemical features of the bottom ashes to ensure environmental sustainability. To this end, batchwise water extraction as promulgated by the European norm EN 12457 or the German DIN 38414-S4 tests is commonly utilized to ascertain the impact of leachable trace elements in bottom ashes on biota. However, the above extraction protocols are not properly simulating the dynamic extraction conditions occurring in the nature, whereby the analytical information provided for risk assessment is debatable.In this work, a downscaled flow-through extraction method is proposed for mimicking the leaching of hazardous trace elements (namely, Pb, Zn, Cd, Cu and Cr) in MSWI bottom ashes by runoff waters more accurately than the manual counterparts. The flow assembly facilitates the full automation of standard and regulatory leaching tests by packing of a suitable amount of solid material into a column, whereupon the leaching reagent is continuously pumped through, thus yielding an accurate assessment of the environmentally significant water-extraction fraction with no effect from readsorption phenomena.The flow-through column system is exploited as a screening tool for fast evaluation of the influence of natural bottom ash weathering on the immobilization of hazardous elements to dictate the potential reuse of the solid waste. The dependence of sorption sites for humic substances on trace element leachability is also discussed. As compared to the steady-state approach, the dynamic method features the substantial shortening of the analytical extraction protocol from 24 h to just 30 min, better precision, with relative standard deviations (R.S.D.) <11% versus >20% R.S.D. for batchwise extraction, improved accuracy because of the absence of metal redistribution phenomena and minimization of manual operations as well as straightforward investigation of leaching rates for the suite of target elements.     

煤中痕量元素在循环流化床锅炉中的迁移行为与富集特性

对天津市某电厂循环流化床(CFB)锅炉燃用的原煤及燃烧产物底灰、飞灰、细飞灰(≤50 μm)进行痕量元素含量的测定,分析了Be、Zn、Hg、V、Cr、Mn、Co、Ni、Cu、As、Se、Cd、Pb 13种痕量元素在燃烧过程中的迁移行为,揭示了痕量元素在CFB锅炉中的分配、富集特性。结果表明,CFB锅炉中,较低的炉温对于痕量元素的迁移富集产生了较大的影响。由相对富集系数得知,Be、V、Co、Se在底灰中耗散,在飞灰中富集,Zn、Mn倾向于在底灰中富集,元素Cd、Pb、Ni、Cu挥发性较强,在底灰和飞灰中均是耗散。As受钙氧化物影响,挥发性表现并不明显。Hg在底灰和飞灰中相对富集系数均很低,表明Hg在整个燃烧过程中以气态形式排放;Hg、As、Se、V、Cr、Mn、Co、Ni、Cu、Zn、Pb均有向小颗粒物中富集的趋势。根据相对富集系数以及研究的13种元素在低温CFB锅炉中的迁移行为,将这些元素分为三类:A类(E_R<0.1),主要是以气态形式排放元素Hg;B类(0.1R≤0.85),较易挥发元素As、Be、Ni、Cu、Se、Cd、Pb、Co、V;C类(E_R>0.85),主要残留在固体产物中元素Zn、Mn、Cr。     

城市污水污泥与固体垃圾混烧过程中重金属迁移特性的研究

通过城市污水污泥与固体垃圾合成样品在小型管式焚烧炉内的混烧实验,采集灰渣样品进行XRF化学成分分析和浸出毒性鉴别测试,结合污水污泥焚烧过程中热力学平衡计算,定量表征了污水污泥中Cu、Pb、Zn、 Mn、Ni在焚烧过程中向底灰、飞灰和烟气迁移的特性及对灰渣的毒性影响。研究结果表明,污水污泥混烧显著提高了飞灰和底灰中重金属含量,其中Zn和Pb增加量最大,而Ni、Mn、Cu依次减少;随着有机氯的加入,飞灰中重金属含量呈现递增趋势,其中Zn表现最明显。毒性测试结果显示,污水污泥的混烧也导致了垃圾焚烧飞灰中Zn和Pb的浸出浓度超过中国对危险废物浸出的控制标准值。同时,重金属迁移的热力学平衡模型预测结果与实验结果差距较大。这表明热力学平衡计算方法还需进一步考虑影响重金属氯化物形成的其他因素,如在焚烧过程中反应动力学、焚烧室内氧气含量变化、与其他元素间的化学反应等。     

A new luminol chemiluminescence reaction using a tetravalent nickel-periodate complex as the oxidant

A modified sequential extraction procedure was developed and applied to characterize the species of metals in fly ash. Two fly ash samples were collected from a coal-fired thermal power plant located in the north of China. A sample was collected from the conventional pulverized coal (PC) combustor and another from the circulating fluidized bed (CFB) combustor. After extraction by the proposed sequential extraction procedure, the elements in the fly ash samples were divided into a water-extractable fraction (F1), an acid-soluble fraction (F2), a reducible fraction (F3), an oxidizable fraction (F4) and a residual fraction (F5). Except for Cu, V, Cd in the PC sample and V, Zn in the CFB sample, most of the other metals were present in the residual fraction (F5), which was very difficult to release into the environment. The fraction distribution patterns in the two samples were also compared. The results indicated that the distribution of metals in different fractions in fly ash samples were probably impacted by different combustion processes.     

A technique for sequential leaching of coal and fly ash resulting in good recovery of trace elements

Coal and fly ash contain many elements. These elements exist in different forms which may change throughout the coal combustion process. There are several processes, including X-ray techniques and leaching techniques by which studies have attempted to assess the form of a particular element in a sample. This work focuses on determining the leachability of selected elements sequentially leached in four extraction solutions: water, 1 M ammonium acetate, 3 M hydrochloric acid and 50% hydrofluoric acid. The emphasis is on evaluating the steps involved in the leaching process with the mass recovery for each element being the basis for evaluation. The total amount of each element that will leach out under the given extraction condition is presented as a fraction of the total present in the material. The materials evaluated were NIST coal and fly ash standards. The elements measured in this study include aluminum, barium, beryllium, calcium, chromium, cobalt, iron, magnesium, manganese, nickel, potassium, sodium, strontium, vanadium and zinc.     

燃煤电厂3种固体废物对水环境影响的研究

以某电厂灰渣作为研究对象,分别对锅炉渣、粉煤灰和烟道灰3种材料对水环境的影响进行了试验,全面分析了灰渣的物理性质和化学成分。分别做了灰渣的浸出毒性试验、浸出剂的pH值对粉煤灰重金属浸出毒性试验,灰渣的腐蚀性、灰渣的淋溶、灰渣的沉降试验,从而得出燃煤电厂固体废物对水环境潜在的毒性影响。     

Leaching Studies of Inorganic and Organic Compounds from Fly Ash

Fly ash is produced in massive quantities by fossil fuel based power plants and waste incinerators, and contains high levels of potentially toxic chemicals. Various leaching tests exist to determine the available fractions, but the outcome is strongly dependent on the experimental conditions, and these have not yet been harmonised at the international level. In order to test existing protocols for heavy metals, several intercomparisons were organised within the framework of an EU-INCO project "ANALEACH", in which seven institutes from five countries participated. Two existing reference materials were made available for the project and test batches of two new fly ash reference materials were produced. Availability tests, leaching tests and pH-stat tests were studied and critical steps in the procedures were identified. Fly ashes can also contain large amounts of inorganic sulphur and nitrogen compounds, and the determination and leaching behaviour of these compounds were also studied. In one intercomparison for metals, inorganic S and N-compounds were also included. A five-step leaching test was optimised for fly ash in order to link metal fractions to different types of binding. Column leaching experiments were carried out to investigate leaching from fly ash into soil, mimicking the effects of (acid) rain on fly ash deposited on topsoil after atmospheric transport. The major fraction of the leached metal ions was retained by the soil. Also large numbers of organic compounds (including many toxic ones) were identified in fly ash extracts, especially in city waste incinerator ash. Leaching procedures based on ultrasonic extraction were developed for organic compounds and an intercomparison exercise was organised. In a field study at the river Nitra(Slovakia) numerous organic pollutants were found at elevated levels downstream from a major fly ash dump site.     

Innovative stabilization/solidification processes of fly ash from an incinerator plant of urban solid waste

Fly ash samples from an incineration plant of urban solid waste (USW) were submitted to a stabilization/solidification process based on encapsulation with a polyester resin. With this process, a very limited increase of about 25% in weight and a compressive strength as high as 1200 kg/cm² can be obtained. The efficiency of the process to stabilize/solidify the residues and to reduce the pollutant release was evaluated by performing both mechanical and leaching tests following the IRSA–CNR standard method. The leaching test was based on treating the sample with an acetic acid solution adjusted to pH 5.2 for 24 h under magnetic stirring. Toxic metals (Pb, Cd, and Cu) and organic pollutants (PAHs, PCBs, and OCPs) were determined in raw fly ash samples and in the leaching solutions of treated samples. Raw residues showed higher concentrations of trace metals than the regulatory limits, whereas the stabilized/solidified residues showed a concentration of all the pollutants lower than the regulatory limits and a compressive strength much higher than the suggested minimum value. Finally, a critical comparison with conventional stabilization/solidification processes based on the use of Portland cement highlighted that the polyester resin-based process performed much better in terms of the release of both organic and inorganic pollutants, thus substantially lowering the environmental impact of these residues.     

煤中微量元素间依存关系的聚类分析

通过对四种不同类型煤中灰分、硫分和１６种微量在不同密度级中呈的Ｒ型聚类分析,研究了煤中微量元素间的依存关系。结果表明：煤中碱土 金属Ｂｅ、Ｓｒ、Ｂａ彼此间的依存关系一般较弱,与所研究的其它元素的相关性也较北：稀土元素Ｌａ、Ｃｅ、Ｙ、Ｓｅ经常相伴而生;Ｖ总与灰分显著相关;Ａｓ、Ｃｏ、Ｎｉ等元素民黄铁矿硫的存在密切相关。     

煤中微量元素在燃烧过程中的变化

在分析微量元素燃烧过程中迁移变化机理的基础上,对电厂用煤和煤灰进行了采样测试,分析了电厂燃煤过程中微量元素的析出变化及在各种灰中的分布富集规律,同时用五个不同的温度段分别对煤进行了燃烧实验,研究了在不同温度下,微量元素从煤中析出的浓度和析出率,通过实验分析,。多数有害微量元素在飞灰中的富集浓度高于其它灰中,燃烧时温度的高低是影响微量的高低是影响微量元素迁移析出的重要因素,温度越高,有害微量元素析出率相对越大。     

300 MW等级燃煤机组煤粉炉与循环流化床锅炉汞排放特性比较

选取某地330 MW煤粉炉(PC炉)和350 MW循环流化床锅炉(CFB)的燃煤电厂进行汞排放特性的研究。采用30B法和安大略法对两个燃煤电厂的除尘器入口、除尘器出口、脱硫塔出口和湿式电除尘器出口的烟气进行了取样和汞浓度分析,采集了入炉煤和副产物底渣、飞灰及脱硫石膏样品。通过样品中汞含量的分布,探讨了PC炉与CFB锅炉机组现有污染物控制设备对汞的协同脱除作用。结果表明,350 MW CFB电厂除尘器出口烟气平均汞浓度降低至0.43μg/m~3,布袋除尘器对汞的捕获效率达到98.9%,相应的燃烧副产物中飞灰是汞的主要富集对象。对于330 MW PC炉电厂,除尘器入口和除尘器出口烟气汞浓度均高于350 MW CFB电厂,烟气汞浓度从除尘器入口、除尘器出口到脱硫塔出口依次降低,在脱硫塔出口烟气汞浓度降低至0.42μg/m~3,静电除尘器和湿式脱硫塔对烟气汞的捕获效率分别为75.0%和22.4%,相应的产物中飞灰和脱硫石膏中汞都有一定程度的富集。     

黑液水煤浆主要矿物元素在炉内的迁移和沉积行为研究

为了研究黑液水煤浆的灰沉积机理，采用沿烟气行程从实验炉不同部位抽取空间灰粒和提取相应位置炉壁灰渣样相结合的方法，并与常规水煤浆相对比，研究了各主要矿物元素（Na、K、Si、Al、Fe、Ca）在烟气流中的迁移趋势和沉积特性。并且通过X射线衍射（XRD）和扫描电镜（SEM）等分析从微观角度进行了验证。结果表明，与常规水煤浆不同的是，Na、Si、Al的迁移和沉积是引起黑液水煤浆沾污结渣的主要矿物元素，灰沉积物中主要包括无水芒硝、霞石等低熔融温度富Na物相，而Fe的沉积是次要因素。