重庆某电厂灰渣中痕量金属元素形态分布研究

本文以某电厂飞灰和灰渣为研究对象，采用Tessier逐级提取分离方法，对零粒物中痕量重金属元素的含量和形态分布进行了研究。结果表明，飞灰中痕量金属元素Hg、As、Co和Cu的含量高于底灰，而Pb、Cd、和Cr的含量则是底灰高于飞灰；五中形态测定值的和与总量测定值基本相当；在煤燃烧形成的飞灰和灰渣中，痕量金属元素主要以稳定态的形式存在，其它形态的含量则比较低。     

煤及其灰渣中的汞

研究了东北、内蒙古东部煤炭中汞的含量分布以及煤中汞向燃烧产物中迁移的规律。煤中汞含量高于土壤,并和煤中全硫分及灰分呈显著正相关。煤中汞在锅炉飞灰中被富集,在底灰中被分散。飞灰粒径越小汞含量越高,显示表面富集特征;飞灰中90％以上的汞存在于＜0.125mm粒子上。飞灰中汞占煤中汞总量23.1％～26.9％,从烟囱排出的汞占56.3％～69.7％,燃煤排放的汞是大气中汞的重要来源     

黔西南煤燃烧产物微量元素分布特征及富集规律研究

通过对黔西南高砷煤及燃烧产物(底灰、粗飞灰、细飞灰和烟气)中微量元素含量、水溶性及赋存状态的测定,分析了微量元素在燃煤产物中的分布特征及富集规律,探讨了燃煤过程中微量元素迁移转化机制.结果表明,As和Sb是黔西南高砷煤的主要危害元素,含量分别为(256±195)μg.g-1和(26±21)μg.g-1.根据元素在燃煤产物中富集程度的差异,将其分为4类:Ⅰ底灰富集型(Cr和W);Ⅱ均匀富集型(Cu和Ba);Ⅲ飞灰富集型(Mn和Mo);Ⅳ细飞灰超富集型(As、Cd、Sb和Pb).As的挥发性强于Sb和Pb.As在细飞灰上表现出强烈的富集;而Sb和Pb在原煤和燃烧产物中的分配具有明显的正相关关系(R2=0.990 1,P<0.05).亲石元素容易在底灰沉积或组成飞灰颗粒基质,亲硫元素燃烧后易于吸附在飞灰颗粒表面.而飞灰颗粒粒径越小,比表面积越大,所吸附的微量元素含量越高.     

重庆某发电厂灰渣中微量元素分布特征研究

本文以某电厂的锅炉灰渣(飞灰和底灰)为研究对象，分析了24个飞灰和24个底灰样品中Hg，As，Se，Pb，Cd，Zn，Ba，Co，Cr，Cu，Li,Ni，V,Zr等微量元素的含量水平和分布规律，结果表明：飞灰中As、Pb、Zn、Ba、Cu、V、Zr和Li的含量大于10ppm，Hg和Cd含量在1ppm以下；与原煤相比，14种元素在飞灰中的含量更高。其中Hg、As、Cu、Ni、Cr、Co、Cd、Zn和V等元素的含量分别是原煤的2倍以上；除As和Se外，其余元素在底灰中的含量高于原煤。     

煤中微量元素的环境效应

以华北某电厂燃煤为例,探讨了煤中微量元素的环境效应评价方法。通过电感耦合等离子体原子发射光谱(ICP-AES)等方法测定了电厂循环流化床炉原煤、飞灰、底灰中F,Pb,Hg,等11种微量元素的含量,通过淋滤实验测得了原煤及底灰中Pb、Hg、Cr等7种微量元素的淋出率,并测定了煤堆附近土壤中Cd、Hg、Cr等6种微量元素的含量,计算出了煤中微量元素对大气、水和土壤环境的污染因子。结果表明,燃煤中元素F、Hg、Se、Cl挥发性较强,燃煤中微量元素对大气环境的综合污染因子达3.5,属重污染。元素Hg、As的淋出率较高,原煤和底灰中微量元素对水环境的综合污染因子分别为0.71和0.88,污染程度属微污染。土壤对Cd、Hg、Pb等元素的富集程度很高,煤中微量元素对土壤环境的综合污染因子为0.98,属微污染。     

燃煤过程中微量元素的分布及逸散规律

本文在采用仪器中子活化（ＩＮＡＡ）和原子吸收法系统测定炉前煤，人工灰化灰，飞灰，底灰中微量元素浓度的基础上，通过对微量元素质量平衡率的计算，进一步研究了燃煤过程中微量元素的分布分配状况和逸散规律，依逸散程度将微量元素分为四类，同时指出某些有毒元素如Ｈｇ，Ｓｅ，Ｍｏ，Ｃｕ，Ｐｂ等散失量较大，值得引起注意。     

煤及其燃烧产物中砷的分布特征

首先研究了我国各主要聚煤区煤中砷的分布,煤的砷含量均值高于世界但低于美国,低于或接近我国土壤砷含量,但与地壳克拉克值比较,砷在煤中被明显富集。从各聚煤区情况看,砷的含量和富集因子均有中新生代煤最大,华南二叠纪煤为次,而华北石炭——二叠纪煤最小的特点。煤各级燃烧产物中砷分布研究表明,底灰中亏损,但富集于飞灰特别是细粒飞灰的表面,质量平衡率的计算显示砷大多能截留于飞灰中,呈蒸气状态逸散入大气的有限。      

含铀煤燃烧底灰中铀的形态分布及其影响因素研究

以云南临沧的含铀褐煤为研究对象,在实验室模拟燃烧试验,考察了不同温度、时间、原煤粒径和是否加入CaO 4种燃烧控制条件下煤的燃烧过程,并采用逐级提取法分析了燃煤底灰中铀的赋存形态,讨论了不同燃烧条件下燃煤底灰中不同赋存形态铀的含量及其相互转化关系。结果表明:燃煤底灰中铁锰氧化物结合态铀和残渣态铀的含量随燃烧温度的升高而增加,碳酸盐结合态铀的含量随燃烧温度的升高而减小;在600℃、不同条件下的原煤燃烧过程中,燃煤底灰中碳酸盐结合态铀和铁锰氧化物结合态铀的质量随燃烧时间的增加逐渐增加,有机物结合态铀和残渣态铀的质量随燃烧时间的增加逐渐减少;原煤粒径较小时,在燃烧过程中易形成飞灰而降低各种赋存形态铀在燃煤底灰中的含量;在原煤燃烧过程中,加入适量CaO会提高燃煤底灰中除离子交换态铀外的各种赋存形态铀的含量,使燃煤底灰中的铀富集。     

干法烟气脱硫副产物中汞的形态分布

通过分析干法烟气脱硫副产物中不同形态汞的含量,研究干法脱硫灰中汞的环境稳定性. 利用逐级化学提取法,分析了锅炉底灰、锅炉飞灰、脱硫塔底灰和除尘器灰中水溶态、酸溶态、过氧化氢溶态及王水溶残渣态汞的含量,研究了不同形态汞含量的变化规律. 结果表明,锅炉底灰、锅炉飞灰、脱硫塔底灰和除尘器灰中w（总汞）分别为0.23,0.36,0.46和1.22 mg/kg,且随着脱硫除尘时间的延长w（总汞）呈增加的趋势,其中,以氯化物、硝酸盐和硫酸盐存在的水溶态汞变化明显,除尘器灰中w（水溶态汞）高达0.72 mg/kg. 分析认为,干法烟气脱硫灰吸附的大部分汞蒸气转化为可溶性的氯化物、硝酸盐和硫酸盐等,另外还有少量汞以单质状态存在.      

利用X射线荧光光谱定量检测飞灰中重金属总量的方法研究

介绍了使用X射线荧光光谱(XRF)分析仪对生活垃圾焚烧飞灰中重金属总量进行定量快速检测的方法。该方法使用标准飞灰样品与空白样品配制成系列标准飞灰试样,采用XRF仪器检测试样,对飞灰中不同元素的特征荧光强度与元素含量进行一元线性回归分析。飞灰中Ba、Pb、Zn、Cr、Cu、As六种元素的拟合方程决定系数(R2)均在0.99以上,Se和Cd元素决定系数依次为0.945、0.989,这八种元素的拟合方程可指导使用XRF定量检测飞灰中重金属总量。Ni和Hg的拟合方程决定系数较低,不建议用于XRF定量检测。     

Occurrence and volatility of several trace elements in pulverized coal boiler

The contents of eight trace elements(Mn, Cr, Pb, As, Se, Zn, Cd, Hg) in raw coal, bottom ash and fly ash were measured in a 220 t/h pulverized coal boiler. Factors affecting distribution of trace elements were investigated, including fly ash diameter, furnace temperature, oxygen content and trace elements‘ characters. One coefficient of Meij was also improved to more directly show element enrichment in combustion products. These elements may be classified into three groups according to their distribution: Group 1. Hg, which is very volatile. Group 2: Pb, Zn, Cd, which are partially volatile. Group 3: Mn, which is hardly volatile. Se may be located between groups 1 and 2. Cr has properties of both group ! and 3. In addition, the smaller diameter of fly ash, the more relative enrichment of trace elements (except Mn). The fly ash showed different adsorption mechanisms of trace elements and the volatilization of trace elements rises with furnace temperature. Relative enrichments of trace elements(except Mn and Cr) in fly ash are larger than that in bottom ash. Low oxygen content can not always improve the volatilization of trace elements. Pb is easier to form chloride than Cd during coal combustion. Trace elements should be classified in accordance with factors.     

Effect of CaO on retention of S, Cl, Br, As, Mn, V, Cr, Ni, Cu, Zn, W and Pb in bottom ashes from fluidized-bed coal combustion power station

This work was conducted to evaluate whether Ca-bearing additives used during coal combustion can also help with the retention of some other elements. This work was focused on the evaluation of bottom ashes collected during four full-scale combustion tests at an operating thermal fluidized-bed power station. Bottom ashes were preferred to fly ashes for the study to avoid interference from condensation processes usually occurring in the post-combustion zone. This work focused on the behaviors of S, Cl, Br, As, Mn, V, Cr, Ni, Cu,Zn, W, and Pb. Strong positive correlations with CaO content in bottom ashes were observed（for all four combustion tests） for S, As, Cl and Br（R = 0.917-0.999）. Strong inverse proportionality was calculated between the contents of Pb, Zn, Ni, Cr and Mn and CaO, so these elements showed association to materials other than Ca-bearing compounds（e.g., to aluminosilicates, organic matter, etc.）. Somewhat unclear behaviors were observed for W, Cu, and V. Their correlation coefficients were evaluated as statistically ＂not significant＂, i.e., these elements were not thought to be significantly associated with CaO. It was also discovered that major enrichment of CaO in the finest bottom ash fractions could be advantageously used for simple separation of elements strongly associated with these fractions, mainly S and As, but also Cl or Br. Removal of5% of the finest ash particles brings about a decrease in As concentration down to 77%-80% of its original bulk ash content, which can be conveniently used e.g., when high As content complicates further ash utilization.     

污泥掺烧对燃煤电厂痕量元素排放特性影响

采用EPA Method 29方法、冷原子吸收光谱法和电感耦合等离子体质谱法采集和分析一台超低排放燃煤机组污泥掺烧前后的原燃料、烟气和副产物样品中各痕量元素浓度,研究污泥掺烧对燃煤电厂痕量元素排放特性的影响.结果表明：污泥中富含Zn、Cu元素,浓度分别是煤样中的18.81倍和17.64倍.污泥掺烧使掺配后入炉煤中痕量元素含量普遍升高.污泥掺烧前后整个系统、锅炉系统和全流程大气污染控制设施的痕量元素质量平衡率均在可接受范围内.污泥掺烧对痕量元素的分布特征无明显影响,随粉煤灰排放是痕量元素的主要排放去向.通过烟囱排放到大气环境的痕量元素排放量占比很小,不超过0.43%.污泥掺烧前后SCR入口烟气中痕量元素除Hg外主要以颗粒态形式存在.污泥掺烧后各痕量元素在粉煤灰和底渣中的相对富集系数未显著改变.经过全流程大气污染控制设施协同控制后,污泥掺烧前后烟囱总排口痕量元素排放浓度分别为0~12.76,0~14.97μg/m³.污泥掺烧后痕量元素排放浓度均满足美国燃煤发电机组有害大气污染物排放标准、上海市燃煤耦合污泥电厂大气污染排放标准和生态环境部生活垃圾焚烧污染控制标准的限值要求.现有的燃煤电厂大气污染控制系统对6%污泥掺烧比工况下痕量元素排放的控制具有较好的适应性.     

电厂煤燃烧后元素硒的分布及对环境的贡献

对电厂煤、除尘器飞灰、渣及不同粒径的烟道飞灰中痕量元素硒进行研究.化学分析表明,硒在渣和除尘器飞灰中亏损而在细飞灰中富集,尤其在>19.0μm的飞灰中明显富集,富集系数达到5.15,造成这种现象的原因一是挥发性元素的挥发-凝结作用,二是燃烧产物在燃烧气流中停留的时间,三与飞灰颗粒形态有关,>19.0μm的飞灰中多孔颗粒可能是造成其富集的原因.逐级化学提取实验表明,煤中硒主要具有机相关性(69.7%),这也是硒挥发性高的一个主要原因;物质平衡计算显示煤中16.5%的硒随气流直接排放入大气,细飞灰中的硒只占1.1%,且大部分在>19.0μm的飞灰中,影响范围小,渣中硒对周围环境的影响更小,飞灰中的硒具有一定的迁移性,也许可以用来改善缺硒土壤.     

Distribution and leaching characteristics of trace elements in ashes as a function of different waste fuels and incineration technologies

Impact of waste fuels (virgin/waste wood, mixed biofuel (peat, bark, wood chips) industrial, household, mixed waste fuel) and incineration technologies on partitioning and leaching behavior of trace elements has been investigated. Study included 4 grate fired and 9 fluidized boilers. Results showed that mixed waste incineration mostly caused increased transfer of trace elements to fly ash; particularly Pb/Zn. Waste wood incineration showed higher transfer of Cr, As and Zn to fly ash as compared to virgin wood. The possible reasons could be high input of trace element in waste fuel/change in volatilization behavior due to addition of certain waste fractions. The concentration of Cd and Zn increased in fly ash with incineration temperature. Total concentration in ashes decreased in order of Zn > Cu > Pb > Cr > Sb > As > Mo. The concentration levels of trace elements were mostly higher in fluidized boilers fly ashes as compared to grate boilers (especially for biofuel incineration). It might be attributed to high combustion efficiency due to pre-treatment of waste in fluidized boilers. Leaching results indicated that water soluble forms of elements in ashes were low with few exceptions. Concentration levels in ash and ash matrix properties (association of elements on ash particles) are crucial parameters affecting leaching. Leached amounts of Pb, Zn and Cr in > 50% of fly ashes exceeded regulatory limit for disposal. 87% of chlorine in fly ashes washed out with water at the liquid to solid ratio 10 indicating excessive presence of alkali metal chlorides/alkaline earths.     

煤及其燃烧产物中有害痕量元素的淋滤特性研究

通过对我国西北部上湾与石嘴山电厂原煤、底灰和飞灰中As、Pb、Cd、Mop、Mo、Co和U等有害痕量元素在不同条件下的淋滤实验,采用原子荧光光谱（AFS）和电感耦合等离子体质谱法（ICP-MS）测定了痕量元素在2套（6个）样品、3种淋滤介质、4个不同时间段获取的淋滤液中的浓度,对比不同元素间淋出率、60h的最大淋出率和淋滤强度的差异性,分析痕量元素在不同条件下的淋滤特性;通过对比元素在原煤和燃煤产物中的含量、60h的最大淋出率以及淋滤液中元素的浓度,参考相关地下水的环境质量标准对痕量元素的环境效应进行了综合评价：As与Se的淋滤性较差,淋滤液中的最大浓度较低,对环境造成危害的可能性很小;Pb与Cd在淋滤液中的最大浓度较高,可能对环境造成危害.Mo与Co的淋出性好,淋出率高,同时淋滤液中的最大浓度是三类地下水环境质量标准的5～10倍,对环境造成危害的可能性最大.     

Bench-scale synthesis of zeolite A from subbituminous coal ashes with high crystalline silica content

In this present work, fly ash and bottom ash with high crystalline silica content were obtained from the coal-fired boilers within the paper industries in Thailand. These coal ashes were used as the basic raw materials for synthetic zeolite production. The crystal type and crystallinity, specific surface area and pore size, and textural properties of zeolite products were characterized by using X-ray diffraction spectroscopy (XRD), N₂ sorption analysis, and Scanning Electron Microscopy (SEM), respectively. It was found that sodalite octahydrate was selectively formed via the direct conventional (one-step) synthesis, whereas through a two-step, sodium silicate preparation and consecutive zeolite A synthesis process, 94 and 72 wt.% zeolite A products could be produced from the fly ash and bottom ash, respectively. The cation-exchange capacity (CEC) of fly ash and bottom ash-derived zeolite A products were closely similar to that of the commercial grade zeolite A.