Effect of unburned carbon content in fly ash on the retention of 12 elements out of coal-combustion flue gas

The aim of this study was to evaluate whether unburned carbon particles present in fly ash can help in the retention of S, Cl, Br, As, Se, Cu, Ni, Zn, Ga, Ge, Rb, and Pb out of flue gas during the coal combustion at fluidised-bed power station where the coal was combusted along with limestone. The competitive influence of 10%-25% CaO in fly ashes on the distribution of studied elements was studied as well to be clear which factor governs behaviour of studied elements. Except of S (with significant association with CaO) and Rb and Pb (with major affinity to Al₂O₃) the statistically significant and positive correlation coefficients were calculated for the relations between unburned carbon content and Br (0.959), Cl (0.957), Cu (0.916), Se (0.898), Ni (0.866), As (0.861), Zn (0.742), Ge (0.717), and Ga (0.588) content. The results suggest that the unburned carbon is promising material in terms of flue gas cleaning even if contained in highly calcareous fly ashes.     

层燃炉燃煤中9种微量元素的迁移

建立了层燃锅炉底灰,飞灰中Ｂｅ,Ｃｏ,Ｃｒ,Ｃｕ,Ｍｎ,Ｎｉ,Ｐｂ,Ｖ,Ｚｒ含量与煤中这９种元素含量关系的经验公式,估算了煤中微量元素在底灰,飞灰和排放大 的烟气中的总量分配。研究了飞灰中元素含量和总量的粒度分布,探讨了煤炭燃烧过程中元素的集散规律。     

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.     

Size distribution of chemical elements and their source apportionment in ambient coarse, fine, and ultrafine particles in Shanghai urban summer atmosphere

Ambient coarse particles (diameter 1.8-10 μm), fine particles (diameter 0.1-1.8 μm), and ultrafine particles (diameter < 0.1 μm) in the atmosphere of the city of Shanghai were sampled during the summer of 2008 (from Aug 27 to Sep 08). Microscopic characterization of the particles was investigated by scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM/EDX). Mass concentrations of Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br, Rb, Sr, and Pb in the size-resolved particles were quantified by using synchrotron radiation X-ray fluorescence (SRXRF). Source apportionment of the chemical elements was analyzed by means of an enrichment factor method. Our results showed that the average mass concentrations of coarse particles, fine particles and ultrafine particles in the summer air were 9.38 ± 2.18, 8.82 ± 3.52, and 2.02 ± 0.41 μg/m³, respectively. The mass percentage of the fine particles accounted for 51.47% in the total mass of PM10, indicating that fine particles are the major component in the Shanghai ambient particles. SEM/EDX results showed that the coarse particles were dominated by minerals, fine particles by soot aggregates and fly ashes, and ultrafine particles by soot particles and unidentified particles. SRXRF results demonstrated that crustal elements were mainly distributed in the coarse particles, while heavy metals were in higher proportions in the fine particles. Source apportionment revealed that Si, K, Ca, Fe, Mn, Rb, and Sr were from crustal sources, and S, Cl, Cu, Zn, As, Se, Br, and Pb from anthropogenic sources. Levels of P, V, Cr, and Ni in particles might be contributed from multi-sources, and need further investigation.     

可溶性磷酸盐处理焚烧飞灰的稳定化技术

对垃圾焚烧飞灰的基本物化性质进行了分析,表明焚烧飞灰的主要元素以Ca、Cl、K、S、Si等为主,另外还含有相当数量的重金属如Pb、Zn、Cu、Mn和Cr等,且Pb、Cu、Zn、Cd等重金属的浸出毒性远高于危险废物浸出毒性标准.研究采用可溶性磷酸盐对焚烧飞灰进行稳定化处理,分别考察了磷酸盐投加量、养护时间和pH值等因素对稳定化产物的影响.结果表明:磷酸盐可以对焚烧飞灰取得很好地稳定化效果,当磷酸盐投加量为3%时,飞灰中重金属Pb、Cd和Zn的浸出浓度能够分别降低97·5%、91·6%和95·5%;养护时间对稳定化产物稳定性的影响不大;稳定化产物能够在相当宽泛的pH范围内保持稳定,其长期稳定化效果很明显.     

贵阳市冬季地表灰尘重金属含量动态变化及原因探析

本研究以贵阳市冬季地表灰尘和家庭燃煤为研究对象,分析了贵阳市冬季不同时段地表灰尘重金属含量的动态变化,以及家庭燃煤取暖排放的煤灰与煤尘对环境中重金属的排放影响.结果表明:贵阳市冬季前后不同时段地表灰尘重金属含量的动态变化规律为:As含量在初冬和晚冬时段均大于初春,Cu和Pb含量表现为晚冬初春初冬,Cd、Ni、Zn在3个时段的含量变化不大;冬季地表灰尘中Cd、Cu、Zn、Pb累积较重;燃煤中元素As、Cd、Pb、Zn主要富集于煤尘中,Ni、Cu则主要富集于煤灰中.贵阳市地表灰尘在晚冬、初春时段,细粒级灰尘所占质量占比明显高于初冬,而且晚冬灰尘中粗粒级所占质量比最低,3个时段中,晚冬时段灰尘中大部分重金属含量随粒级减小而增大的特征表现得最明显.家庭燃煤排放对地表灰尘中的As、Pb含量有一定的影响.     

分级燃烧工况下高岭土对煤中微量元素排放的影响研究

通过在一维煤粉燃烧炉上进行肥煤、无烟煤添加高岭土吸附剂的燃烧实验 ,研究了肥煤、无烟煤及其燃烧产物中 18种微量元素的含量和分布 ;计算了高岭土在分级燃烧工况条件下对每种微量元素的吸附率 .结果表明 :高岭土对中、低挥发性微量元素具有不同的吸附作用 ,吸附效率与煤种、元素种类、燃烧温度等因素有关 ,无烟煤燃烧比肥煤燃烧吸附效果更好 .     

不同pH淋滤条件下飞灰中铬、锌、镍、铅的环境效应

粉煤灰是煤炭燃烧后的副产物,富集于粉煤灰中的微量元素在风化、淋溶等外力作用下极易释放到环境中。pH是影响微量元素淋滤行为的重要因素,利用室内砂箱仿真模拟试验研究不同pH淋滤条件下粉煤灰中微量元素的迁移行为具有重要意义。研究结果表明：不同pH条件淋滤后的粉煤灰中Cr、Zn、Ni和Pb的含量都降低。淋滤后水体中Cr的浓度随着pH的升高呈先增大后减少的趋势,在pH为10时达到峰值;Zn、Ni和Pb的浓度随着pH的升高均呈现先减小后增大的特征。淋滤后土壤中Cr元素含量随pH值的升高表现为先减小后增大;Zn、Ni和Pb含量的变化趋势相似,在pH值为2—6.8时减小,随着pH值的继续升高,在pH为10左右达到峰值,随后下降。粉煤灰在短期淋滤条件下对土壤生态环境影响较小,一般情况下可以忽略。     

An experimental and thermodynamic equilibrium investigation of the Pb, Zn, Cr, Cu, Mn and Ni partitioning during sewage sludge incineration

The effects of different chlorides and operational conditions on the distribution and speciation of six heavy metals (Pb, Zn, Cr, Cu, Mn and Ni) during sludge incineration were investigated using a simulated laboratory tubular-furnace reactor. A thermodynamic equilibrium investigation using the FactSage software was performed to compare the experimental results. The results indicate that the volatility of the target metals was enhanced as the chlorine concentration increased. Inorganic-Cl influenced the volatilization of heavy metals in the order of Pb > Zn > Cr > Cu > Mn > Ni. However, the effects of organic-Cl on the volatility of Mn, Pb and Cu were greater than the effects on Zn, Cr and Ni. With increasing combustion temperature, the presence of organic-Cl (PVC) and inorganic-Cl (NaCl) improved the transfer of Pb and Zn from bottom ash to fly ash or fuse gas. However, the presence of chloride had no obvious influence on Mn, Cu and Ni. Increased retention time could increase the volatilization rate of heavy metals; however, this effect was insignificant. During the incineration process, Pb readily formed PbSiO₄ and remained in the bottom ash. Different Pb compounds, primarily the volatile PbCl₂, were found in the gas phase after the addition of NaCl; the dominant Pb compounds in the gas phase after the addition of PVC were PbCl₂, Pb(ClO₄)₂ and PbCl₂O₄.     

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.     

连环湖阿木塔泡沉积物中重金属形态及其对环境影响分析

采用了BCR三步提取法,对连环湖阿木塔泡AMT岩芯沉积物中的Mn、Cr、Cu、Fe、Ni、Pb和Zn等7种重金属元素的化学形态进行了分析。结果表明：Cr、Cu、Fe、Ni、Pb、zn元素以残渣态为主,Mn元素以可交换态及碳酸盐结合态为主。Cr、Cu、Ni、Pb的有机物及硫化物结合态、Fe—Mn氧化物结合态含量较高,Zn的有机物及硫化物含量较高。其中,Mn、Cr、Ni和Pb对环境产生危害的可能性最大,对这几元素应该予以足够的关注。     

Size distributions and sources of elements in particulate matter at curbside, urban and rural sites in Beijing

Size distributions of 29 elements in aerosols collected at urban, rural and curbside sites in Beijing were studied. High levels of Mn, Ni, As, Cd and Pb indicate the pollution of toxic heavy metals cannot be neglected in Beijing. Principal component analysis (PCA) indicates 4 sources of combustion emission, crust related sources, traffic related sources and volatile species from coal combustion. The elements can be roughly divided into 3 groups by size distribution and enrichment factors method (EFs). Group 1 elements are crust related and mainly found within coarse mode including Al, Mg, Ca, Sc, Ti, Fe, Sr, Zr and Ba; Group 2 elements are fossil fuel related and mostly concentrated in accumulation mode including S, As, Se, Ag, Cd, Tl and Pb; Group 3 elements are multi-source related and show multi-mode distribution including Be, Na, K, Cr, Mn, Co, Ni, Cu, Zn, Ga, Mo, Sn and Sb. The EFs of Be, S, Cr, Co, Ni, Cu, Ga, Se, Mo, Ag, Cd, Sb, Tl and Pb show higher values in winter than in summer indicating sources of coal combustion for heating in winter. The abundance of Cu and Sb in coarse mode is about 2-6 times higher at curbside site than at urban site indicating their traffic sources. Coal burning may be the major source of Pb in Beijing since the phase out of leaded gasoline, as the EFs of Pb are comparable at both urban and curbside sites, and about two times higher in winter than that in summer.     

传统酸浸和微波酸浸处理飞灰重金属的效果及重金属的形态变化特征

采用HCl作为浸出剂,在不同的浸出条件下对垃圾焚烧飞灰中重金属进行浸出试验,并采用连续提取程序对酸浸稳定化处理前后的Cd、Cr、Cu、Mn、Ni、Pb和Zn进行形态分析,研究了传统酸浸和微波酸浸对7种重金属的浸出效率及处理前后的形态变化特征.结果表明,酸浸处理能够有效地从飞灰中提取重金属,浸出效率依次为Zn≈Pb＞Cd＞Mn＞Cu＞Cr＞Ni.微波效应可以明显提高大部分重金属的浸出效率,在液固比(L/S)=25 mL/g、时间7 min和1 mol·L-1HCl条件下Cd、Cr、Cu、Mn、Ni、Pb和Zn的浸出率分别为80.17%、15.05%、58.25%、62.42%、8.88%、89.25%和93.03%.对飞灰酸浸残渣进行的连续提取实验表明,传统和微波酸浸处理后飞灰中重金属的可交换态、碳酸盐结合态和Fe-Mn氧化物结合态明显减少,重金属以残留态存在为主,飞灰稳定性显著提高.     

燃煤电厂中微量元素迁移释放研究

基于原煤、飞灰及底灰的测试分析，对晋北一家燃煤电厂中硫等43种元素向环境的迁移释放作了定量研究，结果表明：Al等30种元素基本留在固体燃煤产物中；As等10种元素部分留在固体燃煤产物中，部分挥发到大气中；元素Br、Hg及硫基本挥发到大气中；各元素的挥发程度与自身的赋存状态及地球化学性质等有关。     

Investigation of basic properties of fly ash from urban waste incinerators in China

Basic properties of fly ash samples from different urban waste combustion facilities in China were analyzed using as X-ray fluorescence （XRF）, scanning electron microscopy （SEM）, X-ray diffraction （XRD）. The leaching toxicity procedure and some factors influencing heavy metals distribution in fly ash were further investigated. Experimental results indicate that the fly ash structures are complex and its properties are variable. The results of XRF and SEM revealed that the major elements （〉10000 mg/kg, listed in decreasing order of abundance） in fly ash are O, Ca, Cl, Si, S, K, Na, Al, Fe and Zn. These elements account for 93% to 97%, and the content of Cl ranges from 6.93% to 29.18 %, while that of SiO2 does from 4.48% to 24.84%. The minor elements （1000 to 10000 mg/kg） include Cr, Cu and Pb. Primary heavy metals in fly ash include Zn, Pb, Cr, Cu etc. According to standard leaching test, heavy metal leaching levels vary from 0 to 163.10 mg/L （Pb） and from 0.049 to 164.90 mg/L （Zn）, mostly exceeding the Chinese Identification Standard for hazardous wastes. Morphology of fly ash is irregular, with both amorphous structures and polycrystalline aggregates. Further research showed that heavy metals were volatilized at a high furnace temperature, condensed when cooling down during the post-furnace system and captured at air pollution control systems. Generally, heavy metals are mainly present in the forms of aerosol particulates or tiny particulates enriched on surfaces of fly ash particles. The properties of fly ash are greatly influenced by the treatment capacities of incinerators or the variation of waste retention time in chamber. Fly ash from combustors of larger capacities generally has higher contents of volatile component and higher leaching toxicity, while those of smaller capacities often produce fly ash containing higher levels of nonvolatile components and has lower toxicity. The content of heavy metals and leaching toxicity maybe have no convincing correlation, and high alkali content of CaO greatly contribute to leaching toxicity of heavy metal and acid neutralization capacity against acid rain.     

黑龙江甘南县大气降尘重金属元素沉降通量及来源分析

从2009年3月到2010年3月,采用被动式同时采集了黑龙江甘南县17个点的大气降尘样品,分析了Cd、Hg、Cr、Mn、Ni、Pb、As、Cu、Zn九种元素的含量,对重金属元素沉降通量进行了计算和分析,并利用富集因子分析和相关性分析的方法对元素来源做了解析。研究表明：降尘中重金属元素Mn的年沉降通量数据值较高,均值为7...     

典型固体废物焚烧飞灰的污染物特性研究

采用成分分析法和毒性监测法系统分析了来源于6类典型固体废物焚烧飞灰的污染物特性．研究表明,6类固体废物焚烧飞灰的主要组成元素有Si、 Ca、 Al、 Fe、 K、 Na、 Cl等．各重金属成分中,Zn是受试飞灰（除LS飞灰）中含量最高的重金属元素,范围在2100～32100 mg/kg,均值达9458 mg/kg;元素Cd、 Zn、 Cu、 Cr、 Ni、 Pb、 As平均值则分别为土壤中的各元素含量的642、 127、 22、 18、 15、 10、 2倍．国标硫酸硝酸法和TCLP浸出程序对飞灰中的重金属浸出率普遍偏低,仅其中2类工业废物焚烧飞灰在TCLP法下超出鉴别限值;虽然受试飞灰中二英类物质（PCDD/Fs）毒性当量均低于危险废物毒性物质含量鉴别(GB 5085.6-2007)有关二英类物质规定,但与浙江省部分地区污染土壤中的平均二英毒性当量进行比较,HZ、 WZ、 NB、 TZ和HUZ飞灰分别为其105、 59、 401、 369和5倍,除LS飞灰外其余5种飞灰的毒性当量值要大大高于加拿大、 新西兰和瑞典的土壤中二英的指导值．本研究结果说明不同焚烧厂飞灰化学组成存在很大差异;焚烧废物成分对飞灰中的重金属元素有一定的影响,但焚烧工艺过程是影响固体废物焚烧飞灰中重金属和二英分布和丰度的最主要因素．因此,无论是生活垃圾还是工业危险废物的焚烧飞灰均具有很大的潜在环境风险,处理或利用前必须对其性质进行充分调研．     

电镀污泥焚烧过程中的热分析以及重金属的迁移规律

选取一种典型的含重金属危险废弃物电镀污泥,研究了电镀污泥的热特性以及不同重金属元素———铅(Pb)、镉(Cd)、铜(Cu)、锌(Zn)、镍(Ni)和锰(Mn)在焚烧产物中的迁移和排放特征.热重分析结果表明,干电镀污泥热重的升温过程中主要有几个失重高峰:100℃,150℃和600℃,其中100℃和150℃主要是电镀污泥中的挥发酚的析出,以及一些有机物质的热解和焚烧,而600℃主要是碳酸盐分解的结果;从能谱分析可知电镀污泥主要由O,S,Al,Ca,Cr,Fe等元素,还有一些次要元素如Mg,Cu,Zn,P,Cl,C组成.升温过程中,非金属元素C和Cl有较为明显的下降,Cr,Fe,Mg在900℃以内变化不大.从迁移规律实验可知,重金属Mn、Pb、Ni和Cu在焚烧过程中随着温度升高含量逐渐降低,其中又以Ni的含量下降最为明显,而Cd则正好相反有明显的富集效应.     

Long-range atmospheric transport of trace elements to southern norway

Results from two investigations of air quality performed in 1978–1979 and 1985–1986 at Birkenes, southern Norway are presentes. The elements Na, Al, Cl, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Ag, Cd, Sb, La and Pb were determined in daily filter samples and data for SO₂ and aerosol sulfate were also collected. The levels in 1985–1986 were lower for most pollution-derived elements than in 1978–1979. This in particular concerned V, Ni, Zn, As, Se, Cd, Sb and Pb, while Br and Sb showed less reduced concentration levels. Sector analysis showed that the main contributing source areas for airborne trace elements in southernmost Norway are southeast to southwest of Birkenes. Comparison of the contributions from different source areas in the two sampling periods indicates that emissions in western Europe had decreased more between the two periods than in eastern Europe. Factor analysis was performed on the two datasets. A five-factor solution revealed the existence of a marine component, a soil component and a general pollution component in the aerosol.     

600MW燃煤电厂痕量元素排放特性实验研究

使用USEPA Method 29方法对600MW燃煤电厂SCR、ESP和WFGD前后4个测点进行烟气痕量元素同时取样,研究了12种痕量元素（Cr、Mn、Co、Ni、Cu、Zn、As、Mo、Cd、Sb、Ba、Pb）的排放特性.结果表明：整个电厂系统、锅炉、SCR、ESP和WFGD中痕量元素的质量平衡率都在可接受范围内,实验结果准确可靠.这12种痕量元素主要分布于ESP飞灰中,相对分布率为69.97%~98.79%.底渣中痕量元素的相对富集指数在0.04~0.51之间,ESP飞灰中痕量元素的相对富集系数在0.3~1.23之间.ESP飞灰中的As、Cd和Pb以及WFGD废水中的Mn、Co和Ni可能会对土壤和地下水产生污染,需要引起关注.12种痕量元素向大气中的排放浓度位于0.02~12.57μg/m³之间,排放因子位于的0.01~2.13g/10¹²J之间,Ni、As、Cd和Pb这4种元素的排放浓度分别达到2.04、0.13、0.02和3.35μg/m³,都远超欧盟空气质量标准中的排放限值,需要加以重视进行限制.