西部煤中环境敏感性痕量元素的燃烧迁移行为

应用仪器中子活化( INAA)、电感耦合等离子体原子发射光谱( ICP- AES)和原子吸收光谱( AAS)对我国西北部五个电厂原煤、底灰和飞灰中环境敏感性痕量元素的含量进行了系统测定,通过不同电厂原煤与燃烧产物中痕量元素的含量变化特征,揭示了痕量元素在不同燃烧产物中的相对富集规律.以痕量元素在不同燃烧产物中的相对富集系数为评价标准,建立了燃烧产物中痕量元素的分配模型.结合痕量元素的原始赋存状态,总结了痕量元素燃烧的迁移富集机理和环境效应.     

Distribution of potentially hazardous trace elements in coals from Shanxi province, China

Shanxi province, located in the center of China, is the biggest coal base of China. There are five coal-forming periods in Shanxi province: Late Carboniferous (Taiyuan Formation), Early Permian (Shanxi Formation), Middle Jurassic (Datong Formation), Tertiary (Taxigou Formation), and Quaternary. Hundred and ten coal samples and a peat sample from Shanxi province were collected and the contents of 20 potentially hazardous trace elements (PHTEs) (As, B, Ba, Cd, Cl, Co, Cr, Cu, F, Hg, Mn, Mo, Ni, Pb, Sb, Se, Th, U, V and Zn) in these samples were determined by instrumental neutron activation analysis, atomic absorption spectrometry, cold-vapor atomic absorption spectrometry, ion chromatography spectrometry, and wet chemical analysis. The result shows that the brown coals are enriched in As, Ba, Cd, Cr, Cu, F and Zn compared with the bituminous coals and anthracite, whereas the bituminous coals are enriched in B, Cl, Hg, and the anthracite is enriched in Cl, Hg, U and V. A comparison with world averages and crustal abundances (Clarke values) shows that the Quaternary peat is highly enriched in As and Mo, Tertiary brown coals are highly enriched in Cd, Middle Jurassic coals, Early Permian coals and Late Carboniferous coals are enriched in Hg. According to the coal ranks, the bituminous coals are highly enriched in Hg, whereas Cd, F and Th show low enrichments, and the anthracite is also highly enriched in Hg and low enrichment in Th. The concentrations of Cd, F, Hg and Th in Shanxi coals are more than world arithmetic means of concentrations for the corresponding elements. Comparing with the United States coals, Shanxi coals show higher concentrations of Cd, Hg, Pb, Se and Th. Most of Shanxi coals contain lower concentrations of PHTEs.     

Geochemical distribution of trace elements in coal: modelling and environmental aspects

The present work consists of verifying a theoretical model based on mass distribution of trace elements in coal. Many versions of the model were tested using 42 elements in 8 different coals (5 American, 2 Brazilian and 1 Spanish). The calculated partial concentrations of elements in organic and inorganic (sulfide, carbonate and sulfate) fractions were obtained. These results could be summarised as following: B, Be, Br, Ge and V are associated to organic coal fraction while As, Cd, Co, Cu, Dy, Hg, Lu, Mo, Ni, Pb, Se, W and Zn occur mainly in sulfide minerals and Ba, Cr, Cs, Ga, Mn, Rb, Sb, Sn, Sr, Ta, U and Zr are distributed in the non-sulfide fraction. Finally, the volatility of trace elements was estimated using the calculated partial concentrations in organic and sulfide fractions. The applicability of this parameter in related environmental problems was discussed, comparing model results with experimental and theoretical literature data of the mobilisation of these species into atmosphere.     

The fate of trace elements in fluidised bed combustion of sewage sludge and wood

Combustion tests have been carried out in a fluidised bed boiler to investigate the fate of trace elements during co-combustion of wood and municipal sewage sludge. The approach was to collect fuel and ash samples and to perform thermodynamic equilibrium calculations for gasification (reducing) and combustion (oxidising) conditions. Trace elements are found in the ash. Even most of the highly volatile Hg is captured in the bag filter ash. The bag filter ash offers higher surface area than the secondary cyclone ash and enhances the capture of Hg. There is no obvious correlation between capture and parameters investigated (sludge precipitation agent and lime addition). As, Cd, Hg, Pb, Se, Sb and Tl are predicted by equilibrium calculations to be volatile in the combustion chamber under oxidising conditions and Hg even at the filter temperature (150 °C). Reducing conditions promote, in some case more than others, the volatility of As, Cd, Pb, Sb, Se, Tl and Zn. The opposite effect was observed for Cu and Ni. Data points to the necessity of including bag filter in the gas cleaning system in order to achieve good removal of toxic trace elements.     

大同侏罗纪10-11#煤中微量元素分布赋存特征

讨论了大同 1 0 - 1 1 #煤中 36种微量元素的含量分布 ,通过浮沉试验及煤岩组分定量统计 ,运用 Salori方法 ,计算了 1 4种有害微量元素在大同煤不同煤岩组分中的分布 ,进而分析了其赋存状态及其在煤炭洗选过程中的脱除潜力 .结果表明 ,大同煤中大部分微量元素含量较低 ,但As,Hg,Cr,Sb等元素的有机组分含量偏高 ;大部分微量元素主要分布于矿物中 ,而 B,Be,Cd,Co,Ni和 Sb等有害元素含量偏高 ;同时 ,相对而言 ,As,B,Ba,Cd,Co,Cr,Mn和 Ni等元素在镜质组中含量较高 ,而 Be,Li,Pb和 Sb等元素在丝质组中含量较高 .浮沉试验表明 ,微量元素在煤炭洗选过程中的迁移、脱除行为主要受其赋存特征影响     

Partitioning of elements in a entrained flow IGCC plant: Influence of selected operational conditions

The partitioning of trace elements and the influence of the feed conditions (50:50 coal/pet-coke feed blend and limestone addition) was investigated in this study. To this end feed fuel, fly ash and slag samples were collected under different operational conditions at the 335 MW Puertollano IGCC power plant (Spain) and subsequently analysed. The partitioning of elements in this IGCC plant may be summarised as follows: (a) high volatile elements (70->99% in gas phase): Hg, Br, I, Cl and S; (b) moderately volatile elements (up to 40% in gas phase and ?60% in fly ash): As, Sb, Se, B, F, Cd, Tl, Zn and Sn; (c) elements with high condensation potential: (>90% in fly ash): Pb, Ge, Ga and Bi; (d) elements enriched similarly in fly ash and slag 30-60% in fly ash: Cu, W, (P), Mo, Ni and Na; and (e) low volatile elements (>70% in slag): Cs, Rb, Co, K, Cr, V, Nb, Be, Hf, Ta, Fe, U, Ti, Al, Si, Y, Sr, Th, Zr, Mg, Ba, Mn, REEs, Ca and Li. The volatility of As, Sb, and Tl and the slagging of S, B, Cl, Cd and low volatile elements are highly influenced by the fuel geochemistry and limestone dosages, respectively.     

Formulation of muds for pelotherapy: effects of “maturation” by different mineral waters

Spa centres in northern Italy use clayey admixtures for the formulation of muds to be used in pelotherapy. The basic ingredient (“virgin” clay) is a dressed bentonitic geomaterial with mineralogical composition: smectite 60–70%, illite 5–10%, kaolinite 10–15%, quartz 5–10%, calcite 5–10% and feldspars 2–3%.The peloid muds are obtained by “maturation” of the virgin clay with mineral waters gushing out in situ which have different geochemistry: sulphureous, Ca-sulphate, Ca–Mg-sulphate and Br–I-salty (after the Italian regulation DPR 105/92). The maturation treatment is varying with respect to the mixing procedure and lasting time.Peculiar parameters have been tested to verify the effects of various maturation treatments, i.e., changes with respect to virgin clay.Formation of organic matter is due to the presence of microorganisms and algae in the maturation habitat. The <2 μm fraction is generally decreased due to clay particles agglomeration. Mineralogical changes are mainly concerning the degradation of clay minerals, as smectite and illite, and subordinately to the dissolution of calcite. Cation exchange capacity (CEC), soluble salts, water retention, swelling index, activity, consistency parameters (WL, WP and PI), thermal behaviour and cooling kinetics are influenced by the geochemistry of mineral waters used for the maturation treatments but with some opposite trends for Br–I-salty water, and for sulphureous and Ca-sulphate waters, respectively.Noteworthy was the influence of high-pH value of the virgin clay on the pH of peloid muds (in fact, the pH of the used mineral waters is ranging around the natural value). Furthermore, the temperature reached by the peloid muds after 20 min of application (calculated after an innovative mathematical model) is influenced by water retention. An increase in plasticity index and a slower cooling are considered to improve the quality of the obtained peloid muds for pelotherapy.The observed different cation exchange behaviour and soluble salt content could be discriminant for either dermatological masks or thermal body cataplasms.A need of regulation (standard procedures) is suggested to certificate the clay geomaterials suitable for pelotherapy and also for drugs formulation.     

Volatility and chemistry of trace elements in a coal combustor

The volatility of 16 trace elements (TEs) (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Se, Sn, Te, Tl, V, Zn) during coal combustion has been studied depending on the combustion conditions (reducing or oxidizing) and type of coal (high- or low-ash coal), together with their affinities for several active gaseous atoms: Cl, F, H, O, and S.

The elements can be divided into three groups according to their tendencies to appear either in the flue gases or in the fly ashes from a coal combustor:

Group 1: Hg and Tl, which are volatile and emitted almost totally in the vapor phase.

Group 2: As, Cd, Cu, Pb and Zn, which are vaporized at intermediate temperature and are emitted mostly in fly ashes.

Group 3: Co, Cr, Mn and V, which are hardly vaporized and so are equally distributed between bottom ashes and fly ashes. In addition, Sb, Sn, Se and Te may be located between Groups 1 and 2, and Ni between 2 and 3.

At 400 and 1200 K, the 16 TEs behave differently in competitive reactions with Cl, F, H, O and S in a coal combustor.     

Trace element evaporation during coal gasification based on a thermodynamic equilibrium calculation approach

Thermodynamic equilibrium calculations using the HSC-Chemistry program were performed to determine the distribution and mode of occurrence of potentially toxic and corrosive trace elements in gases from coal gasification processes. The influence of temperature, pressure and gas atmospheres on equilibrium composition was evaluated. In these reducing conditions, the behaviour of the trace elements is complex, but some form of organization can be attempted. Elements were classified into three groups. Group A includes those elements that, according to thermodynamic data at equilibrium, could probably be condensed in coal gasification. Mn is classified in this group. Group B contains those elements that could be totally or partially in gas phase in gas cleaning conditions, and can be divided into two subgroups, depending on whether the cleaning conditions are hot or cold. Co, Be, Sb, As, Cd, Pb, Zn, Ni, V, Cr are elements in this group. Group C contains those elements that could be totally in gas phase in all the possible conditions, including flue gas emissions. Se, Hg and B are the elements that make up this group.     

Thermodynamic equilibrium study of trace element transformation during underground coal gasification

In order to provide theoretical basis for gas cleaning and pollution control thermodynamic equilibrium calculations were performed to predict the partitioning of trace element species under special conditions for underground coal gasification, including both oxygen-steam gasification and air blown gasification under elevated pressures. The trace elements studied include As, Se, Pb, Ni, Cd, Cr, Sb. The results indicate, in the condition of large-section UCG process with oxygen-steam injection, all the elements studied present in the gas phase during gasification stage. Ni and Cr are hardly volatile and tend to condense below 1000 °C. Most of them will be enriched in bottom ash. As, Pb, Cd, Sb totally or partially occur in gas phase in underground gas cleaning system. In cold cleaning system, they exist in condensed phases and tend to be enriched in fly ash, which is beneficial to trace element removal. Se presents in gas phase in the form of H₂Se(g) even in ground cold gas cleaning system. The presence of potassium makes arsenic less volatile due to the formation of K₃AsO₄ and selenium is not affected. Also the amount of gaseous antimony chloride is reduced because of prior formation of alkali metal chloride. Pressure shows a remarkable effect on equilibrium partitioning of As, Se, Sb. With rising pressure, increasing quantities of hydrides of these trace elements are generated due to the enhancement of the reducing atmosphere. At the same time, the condensation points of all the trace elements sharply increase with pressure. It is found that for underground air blown gasification, the gaseous species of trace element sulfide can be easily formed, and the trace elements have lower condensation points than those for oxygen-steam gasification.     

Trace element behaviour in the Sasol-Lurgi MK IV FBDB gasifier. Part 1 - The volatile elements: Hg, As, Se, Cd and Pb

Coal-fired power and heat production are the largest single source of Hg in the atmosphere, and in March 2005, the US-EPA ruled regarding Hg reduction from coal utilization in the USA. Appropriate Hg pollution control of technology, as well as reductions in the uses of Hg and coal-containing Hg can readily reduce the releases of Hg from coal utilities. Integrated multi-pollutant (SOx, NOx, particulate matter and Hg) control technologies may be a cost-effective approach. Prior to considering mitigation technologies, it is necessary to understand the quantity of mercury in the feed coal, its mode of occurrence (i.e. mineral or organic associations), its partitioning behaviour during the process, and the volume and species in which it is being emitted via stacks. These factors have all been investigated up to the point of release for the Sasol gasification and steam-raising plants, including other trace elements.The focus of this paper is to discuss the more recent environmental research developments by Sasol, where trace element simulation and validation of model predictions have been undertaken for the Sasol-Lurgi gasification process operating on lump coal. Fact-Sage thermodynamic equilibrium modeling was used to simulate the trace elements: Hg, As, Se, Cd and Pb gas phase and ash phase partitioning and speciation behaviour occurring in a fixed-bed pressurised gasifier. A Sasol-Lurgi Mark IV (MK IV) fixed-bed dry bottom (FBDB) gasifier was mined via turn-out sampling in order to determine the trace element changes through the gasifier, findings being used to validate the modeled results. This paper will focus on the behaviour of the volatile Class I trace elements: Hg, As, Se, Cd and Pb within the Sasol-Lurgi MK IV FBDB gasifier as function of coal quality. This study excludes the downstream gas cleaning partitioning and speciation behaviour of these elements, which will form the basis of a future paper.Good agreement between model-predictions and measurements have been attained in this study, with the exception of As. Hg, Cd, Pb, As and Se were all found to be highly volatile, partitioning into the gas phase. Hg was found to be the most volatile element during fixed-bed gasification and is present in the gas phase in the form of elemental Hg (g). As, Se, Cd and Pb have lower volatilities when compared to Hg, and they vary in an order: Hg > Se > Cd > Pb > As. Speciation predictions showed that: Hg, AsH₃, H₂Se, PbSe, Cd, CdS, and PbS/Pb/PbCl, species could potentially exist in the raw gas phase.     

Volatilisation of trace elements for coal–sewage sludge blends during their combustion☆

The influence of sewage sludge addition on the volatility of 37 trace elements (Ag, As, Au, B, Ba, Bi, Cd, Ce, Co, Cr, Cs, Cu, Ga, Hf, Hg, La, Li, Mn, Mo, Nb, Ni, Pb, Rb, Sb, Sc, Se, Sn, Sr, Ta, Te, Th, Tl, U, V, Y, Zn, Zr) during coal combustion was studied. For this purpose, a bituminous coal from the Asturian Central Basin and sewage sludge treated with Ca(OH)₂ and FeCl₃, as well as 10 and 50 wt% sludge–coal blends were used. Combustion experiments were performed in a laboratory electric furnace at 800, 900, 1000 and 1100 °C. The results have confirmed that the high Cl contents of the sludge can produce a pronounced effect on the volatilisation of some trace elements (Ag, Cd, Cs, Cu, Li, Pb, Rb and Tl) due to the probable formation of volatile chlorides, while the high CaO concentrations increase the retention of some elements in ash as As, Se and Te. The above opposite effects of Cl and CaO on trace element volatilisation were generally inappreciable for the 10 wt% blend, while they were more significant, but not as noticeable as expected, for the 50 wt% blend.     

ICP-OES测定玩具新指令第三类物质17种可迁移元素

本实验通过试验,对ICP-OES仪器工作条件进行了选择和优化,建立了ICP-OES测定欧盟玩具安全新指令限制第三类物质的17种可迁移元素（铝、锑、砷、钡、硼、镉、铬、钴、铜、铅、锰、汞、镍、硒、锶、锡、锌）的方法。本方法的检出限低,选取的第三类物质：涂层、聚合物、纸张、纺织品、金属、木材等多种材料的平均回收率均在94%~109%。结果显示方法有良好的准确度。     

Mobility of trace elements from selected Australian fly ashes and its potential impact on aquatic ecosystems

Batch leaching tests have been performed on fly ashes collected from four Australian power stations fuelled by chemically different coals. Two acidic and two alkaline fly ashes were subjected to long-term (144 h) leaching tests, and the behaviour of As, B, Mo and Se was investigated to obtain data on their potential for mobilisation during fly ash-water interactions. All four elements are mobile under different conditions and over different leaching times. The concentrations of these elements released in leaching solutions with initial pH values of 4, 7 and 10 were used to assess the influence of pH conditions on element mobility from the acidic and alkaline fly ashes. The most mobile of the four elements leached were Mo from alkaline fly ashes and B from acidic fly ashes. Arsenic concentration increased with time in leachate solutions from acidic and alkaline fly ashes; however, in solutions in contact with alkaline fly ashes the As concentration, after reaching a maximum, later decreased with time. Selenium mobility shows a similar pattern to that of As, with similar leaching concentrations. Boron has the highest relative mobility of all four elements. A process possibly responsible for the decrease in concentration of B, As and Se in alkaline leaching solutions is the formation of ettringite. Equilibrium between the solid phase (ash) and the leaching solution was not reached in any of the leaching experiments. The pH of the leaching solution is the key factor affecting the mobility of these trace elements in these fly ashes.     

Trace elements (Mn,Cr, Pb,Se, Zn,Cd and Hg) in emissions from a pulverized coal boiler

The concentrations of seven trace elements (Mn, Cr, Pb, Se, Zn, Cd, Hg) in raw coal, bottom ash and fly ash were measured quantitatively in a 220 tons/h pulverized coal boiler. Factors affecting distribution of trace elements were investigated, including fly ash diameter, furnace temperature, oxygen concentration and trace elements' characteristics. Modified enrichment factors show more directly element enrichment in combustion products. The studied elements may be classified into three groups according to their emission features: 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 Groups 1 and 3. The smaller the diameter of fly ash, the higher is the relative enrichment of trace elements (except Mn). Fly ash shows 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 concentration will not always improve the volatilization of trace elements. Pb forms chloride more easily than Cd during coal combustion.     

Volatile trace element behaviour in the Sasol fixed-bed dry-bottom (FBDB)™ gasifier treating coals of different rank

Trace element simulation and validation of model predictions for the elements Hg, As, Se, Cd and Pb have recently been undertaken for the Sasol^® FBDB™ gasification process operating on lump coal. The validation was conducted by interpolating the residual trace elements content remaining behind in the solid coal/char/ash fractions after sequential mining of a quenched commercial-scale gasifier operating on low rank grade C bituminous Highveld coal used for gasification in South Africa. This paper extends the research understanding by comparing the volatile trace element behaviour of these same elements, using the same gasification technology, but operating on North Dakota lignite. The focus will be on the behaviour of the volatile Class III trace elements: Hg, As, Se, Cd and Pb within the Sasol^® FBDB™ gasifier as function of coal rank. This study excludes the downstream gas cleaning partitioning and speciation behaviour of these elements.Findings indicate that although the feed concentration and mode of occurrence of these elements differ quite substantially between the two coal types studied, that the volatilization profiles of the elements are indeed quite similar; being within 0.1%-15% lower in the case of the lignite when compared to the bituminous coal. In both cases, Hg was found to be the most volatile and As the least; with the volatility order varying slightly for the metals Se, Cd and Pb for the two coal types. The differences observed in the trace element volatilization rate are supported by the temperature profile which was inferred from the reflectance of vitrinite (RoV) measurements of the dissected fuel bed material. The highly reactive lignite, is successfully gasified at a lower temperature than is the case for bituminous coal using the Sasol^® FBDB™ gasification process. Speciation predictions have earlier shown that: H₂ Se, CdS, PbS/Pb/PbCl, and AsH₃ species possibly exist in the gas phase. In reality, organically-associated trace elements will also be volatilized into the gas phase, but due to a lack of thermodynamic data for the lignite organo-metallic species at this stage only inorganic associations could be modelled.     

Prediction of trace element volatility during co-combustion processes

The behaviour of some selected trace metals (Hg, Cd, As, Pb, Sb, Cr, Co, Cu, Mn, Ni and V) during co-combustion processes of bio-waste materials (sewage sludge, waste wood, refused derived fuel) and coal has been predicted by thermodynamic equilibrium calculations using the HSC-Chemistry 4.0 software. The influence of temperature, flue gas composition, trace element concentration and minor fly ash components on equilibrium composition was evaluated. For most of the elements, an increase in the HCl concentration favours the formation of gaseous species while increasing concentration of SO₂ in the gas composition enhances the formation of condensed species. Trace element interactions with minor fly ash components were predicted. From results obtained in this study it may be concluded that, from a thermodynamical point of view, the addition of a secondary fuel in combustion processes does not produce an increase in trace element emissions to the environment. Generally, trace elements are captured in ashes avoiding that these elements reach the stack.     

Distribution of toxic elements in the products of the extraction of bitumens from coal and peat

The effect of bitumen extraction conditions on the behavior of a number of toxic trace elements (V, Cr, Ni, Cu, Zn, As, Sb, and Pb) in solid fossil fuel samples was studied. It was found that the capacity of fossil fuels to concentrate trace elements can be monitored and the type of compound can be determined based on the dimensionless quantities of carbophilicity and concentration factors of the trace elements in coal and peat. The types of compounds in fossil fuels were found and graphically represented for the test trace elements.     

Trace elements in black and oil shales

Data on the abundance of trace elements in oil and black shales, as well as and the average concentrations of trace elements in these caustobioliths, are considered. In general, oil shales are enriched in Li, Be, B, Rb, Ta, and Se and depleted in Mo, Re, Ag, Au, V, Th, Cu, Hg (and, perhaps, W, As, and U) relative to black shales. Tentative values of minimal concentrations of trace elements oil shales are presented that make the integrated processing of shale organic matter economically viable to obtain by-product concentrates of valuable trace elements useful as feedstock for their recovery.     

新疆不同产地沙枣叶微量元素测定及主成分分析

为了测定新疆不同产地沙枣叶中Li、Na、Mg、K、Al、Ca、Fe、Cr、Mn、Cu、Zn、As、Se、Sr、Ag、Cd、Hg和Pb 18种微量元素的含量,利用微波消解法对沙枣叶样品进行前处理,采用ICP-MS测定沙枣叶中18种微量元素的含量,运用主成分分析法并结合SPSS软件对测定结果进行综合分析.结果显示,检测到新疆不同产地沙枣叶中Na、Mg、K、Ca、Fe、Mn、Zn、Sr、Se的含量相对较高,未检测到重金属元素Hg、Ag,这18种元素的加标回收率为95.8％ ～ 102.3％,相对标准偏差＜3.3％.最终主成分分析选出9个主因子,得出沙枣叶的特征元素为Mg、Al、Fe、Cu、Cd、K、Se.喀什地区沙枣叶品质总体高于其他7个产区.本方法能够准确、可靠地测定沙枣叶中微量元素的含量,具有较高的灵敏度,可用于沙枣叶中微量元素的测定,为沙枣叶的深度开发利用以及产区考核提供了参考依据.