煤中微量有害元素洗选洁净的研究进展

阐述了煤中微量有害元素的赋存状态和洗选脱除机理,指出微量有害元素在选煤过程中的迁移行为取决于其赋存状态和有机亲和性,以无机态或矿物质结合态为主的有害元素大部分能被脱除,总结概括了常规洗选方法脱除煤中微量有害元素的研究状况,指出常规洗选方法一定程度上脱除煤中微量有害元素,重点分析了磁选脱除煤中有害微量元素的研究进展.     

煤中有害微量元素的洁净潜势分析

为降低煤中有害微量元素含量,提高商品煤质量,以大河边矿原煤为对象进行分步释放浮选试验,测定有害微量元素在分步浮选产物中的含量,研究矿物质的迁移特征;对4个选煤厂的8个煤样采用电感耦合等离子体质谱测定其中有害微量元素含量,计算有害微量元素脱除率,研究有害微量元素的迁移特性和洁净潜势。结果表明,煤中矿物质大多集中在灰分中,基本可以随灰分的脱除而脱除;有害微量元素与矿物质之间的相关系数均大于0.708,说明两者存在高度相关性。煤中有害微量元素大多数以无机矿石的形态赋存,其迁移规律主要受控于无机矿物的迁移,少数有害微量元素以有机态存在,普通物理分选对其脱除效果较差;还有一些有害微量元素赋存状态多样,脱除率表现在较宽范围内。     

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     

毕节地区煤中微量有害元素的初步分析

分析了煤中微量有害元素研究的目的、意义,叙述了国内外对每种微量元素研究的历史和现状,提出对毕节地区煤微量有害元素中研究的方法。     

煤品质变化及有害元素迁移的研究进展

为了探明煤炭在转移、储存过程中品质指标(如水分、灰分、发热量)的波动以及煤中有害元素在煤炭周转、利用过程中的迁移和转化,综述了目前国内外煤炭物流、存储中品质变化的研究进展,对煤中有害元素迁移的相关研究进行梳理。结果表明:煤炭在物流环节中品质指标会出现一定范围的波动,影响了煤炭的生产和销售;煤中有害元素在煤炭周转、利用过程中发生迁移和转化,造成了严重环境污染;事前控制,即煤炭分选,在提高煤热值,降低了煤中硫分、灰分的同时,有效脱除了微量有害元素;明确煤质变化的规律,探究煤中微量有害元素迁移的原理和规律,有利于煤炭的合理开发、环境质量的有效控制。     

毕节地区煤及粉煤灰中微量有害元素分析

煤及粉煤灰中微量元素的研究意义重大和广泛。当前人们最为关注的是资源利用和环境污染两个方面。在我国，煤炭的产量和消耗巨大，研究煤及粉煤灰中微量元素的环境效应更具现实意义。从几种微量有害元素对环境、人类以及动物的健康的危害，以及毕节地区特殊的地质条件地理环境气候特征等方面说明对毕节地区煤及粉煤灰中微量有害元素分析的必要性。     

煤中有害微量元素及其在加工转化中的行为研究进展

从成因上论证了煤中有害微量元素存在的必然性,基于有害微量元素在煤中的赋存特征,评介了开采、洗选、燃烧、热解、气化等过程中煤中有害微量元素迁移、转化的研究现状,指出气化过程中煤中有害微量元素演变研究中的不足,强调加强有害微量元素在典型气化工艺过程中迁移转化规律与污染防治方法研究的必要性,针对相关领域研究各自独立、衔接不紧的问题,提出从煤炭全生命周期的角度对有害微量元素展开整体性研究或为煤中有害微量元素未来的研究方向。     

煤加工利用过程中有害微量元素迁移控制措施

绝大多数煤中含有有害微量元素,在煤加工利用过程中迁移析出,且我国是产煤大国,每年有80%的煤被用于直接燃烧,这些元素累积到一定程度会对人体健康及生态环境产生巨大负面影响。针对这一问题,分三个阶段(燃烧前、燃烧中、燃烧后)对煤中有害微量元素迁移规律进行阐述,并提出相应的控制措施。     

微波协同化学助剂强化脱除煤中硫

硫是煤中主要有害元素,煤炭利用过程中硫的排放是酸雨的重要成因,脱硫是煤炭洁净利用的研究热点之一。微波具有促进反应发生、加快反应速率的作用,微波协同化学助剂脱硫是煤炭脱硫的重要手段。本文通过微波辐照结合3种化学助剂研究煤中硫的脱除效果,利用正交试验考察微波辐照时间、化学助剂种类和煤种对脱硫效果的影响。结果表明,煤种对微波协同不同助剂的脱硫效率影响较大,所选3种煤样的最佳辐照时间各不相同;硝酸与微波联合的脱硫效果最好,其中贵州(GZ)煤在微波协同硝酸作用下,全硫脱除率可达71. 2%。形态硫测试分析表明煤样经脱硫后无机硫脱除效率较高,最高可达90. 5%,有机硫脱除效率在20%～40%。XRD谱图分析显示微波协同化学助剂脱硫后,煤中主要矿物和煤质结构没有明显变化,微波在脱除煤中硫分的同时可保持煤炭基质稳定。XPS谱图分析表明,煤样硫醚(醇)类有机硫脱除效果较好,脱除率可达49. 4%,亚砜类略低,脱除率为23%～28%,噻吩类有机硫脱除效果最差,脱除率在10%～20%。     

关于煤炭高效洁净利用中的应用基础研究

阐述了煤高效、洁净利用基础研究的重要性,介绍了中国煤炭利用的概况,分析了国内外在这一领域的研究工作现状.提出了煤的分子结构、孔结构、煤中有害元素赋存与脱除、煤转化工艺及催化反应中基础研究及煤制高聚物单体和碳材料等6项内容.     

Production of clean fuels by solvent skimming of coal at around 350 °C

The authors have recently presented a new coal extraction method by which various kinds of coals ranging from brown coals to bituminous coals could be extracted up to 80% of the parent coals in a flowing stream of tetralin or a coal derived oil, carbol oil, under 10 MPa at 350 °C. The extract obtained by this method was almost free from inorganic materials. In this study the effect of solvent recycling on the extraction behavior was examined to make the method practically applicable. The solvent recycling was found to be effective in enhancing the extraction yield and in decreasing further the inorganic fraction in the extract. The extract and residue obtained were characterized through various analyses. To examine how inorganic materials are removed by the extraction, the contents of inorganic elements, including harmful trace elements, in the extract were investigated. It was clarified that the presented method was effective in the removal of most of the inorganic elements including even harmful trace elements from coals, although the degree of removal was dependent on the kind of element.     

Mineral matter and elemental concentrations in selected western canadian coals

Major and trace element analyses were performed on coals from various locations in western Canada, and on low-temperature (150 °C) and high-temperature (1000 °C) coal ash produced from these coals. Elemental analyses were carried out by X-ray fluorescence spectroscopy and intense neutron activation analyses. Based on their trace elements, the coals in this study fall into two groups: 1. low-rank coals (lignite-subbituminous) of late Cretaceous and Tertiary age; and 2. high-rank coal (bituminous-semianthracite) of Jurassic-Cretaceous age. The elemental analyses of the coals and coal ash indicate that the local conditions had considerable influence on the concentrations of certain trace elements.Antimony and selenium in coals are the only elements which are enriched relative to concentrations in the earth's crust; arsenic is concentrated in lignite to subbituminous coal, but is depleted in bituminous-anthracite coals; as expected the ash of these coals showed many more instances of enrichment.     

Organic sulfur and hap removal from coal using hydrothermal treatment

Coal is still the major source of power for electrical generation worldwide and will continue to be in the foreseeable future. However, the inorganic elements in coal that qualify as hazardous emissions upon combustion of the coal become an increasingly important concern. Primary emphasis has been on postcombustion cleanup of these emissions, with no technology achieving overwhelming success. The precombustion technique reported here shows promise for removing trace elements as well as sulfur prior to burning the coal. This study shows that hydrothermal treatment need not be carried out at extreme conditions to effect such removal. The sulfur content and selected trace elements of some coals are reduced by 50% or more by water at conditions above the critical temperature but below the critical pressure. The study also shows that the technique was more effective on some coals than others. Results from a pilot-scale test are included in addition to bench-scale data.     

Semi-quantitative ESCA examination of coal and coal ash surfaces

Four North American coals and their ashes were examined using the direct, surface sensitive technique of X-ray photoelectron spectroscopy (ESCA). Two US National Bureau of Standards reference coals (SRM 1632a, SRM 1635) and one ash (SRM 1633a) were used for instrument calibration. These results verified the semi-quantitative nature of ESCA and its previously determined element detection level of ≈ 10^?9 gm cm^?2 of surface (≈0.1 bulk wt%). Thus, major elements and surface concentrated trace elements were detectable for these samples. ESCA detected elements present in the coal and/or ash in different chemical environments, for example sulphur as the sulphide or sulphate and carbon as graphite, carbonyl, carboxyl or hydrocarbon. The results of this preliminary study indicate that ESCA is useful to elucidate element siting within coal; information that is difficult to determine by analytical techniques requiring sample destruction prior to analysis. Several raw coals contained fluorine and chlorine near the one per cent level. Ashing effectively concentrates the mineral fraction of a coal by an order of magnitude resulting in additional elements being detected by ESCA. The resultant detection level of elements in the original coal is thus lowered to ≈0.01 bulk wt% by ashing. It was found that fluorine and sulphur were highly concentrated on several coal ash surfaces possible indicating surface Sorption reactions during combustion. Application of ESCA in coal geochemistry and mineralogy is indicated by this study. ESCA has the potential to measure elements at the minor and possibly trace level and confirm element siting within coal and coal ash. In addition, it may be possible to identify coals from different deposits by their unique broad scan ESCA spectra fingerprints.     

Trace elements in coal: Associations with coal and minerals and their behavior during coal utilization - A review

Trace elements such as mercury, arsenic and selenium present in coal are known to be of concern for public health. Coal-fired power plants have resulted in emission of several tons of TEs in environment. These elements mostly evaporate during combustion and condense either homogeneously as sub-micron ash or heterogeneously onto already existing fine ash. The coal-mineral and mineral-mineral associations play an important role in the formation of fine particles and in subsequent condensation of trace elements in various phases. Any retention of these elements in fly ash particles is strongly influenced by their association with other minerals in individual coal and mineral grains. Clean coal technology development is, therefore, a priority area for research and needs continuous improvements in increased efficiency and decreased pollutant emission. The paper will include trace elements in different coals from around the world. It will consider different modes of occurrences present in coals, the ash formation and evaporation of trace elements and emissions. The typical emissions from typical power stations will be presented. The paper will also review different approaches adopted in estimating the deportment of these elements. The paper at the end would discuss control strategies for reducing emissions and future directions.     

Trace element partitioning during the firing of washed and untreated power station coals

The effect of coal washing on trace element content and combustion behaviour of four world-traded coals has been studied at rig scale. The inputs and process outputs from a 1 MW combustion test facility, including coal, bottom ash, suspended fly ash, retained ash and flue gas, have been analysed for a standard suite of 17 trace elements. The results suggest that although coal cleaning significantly reduces the total ash content of the coal, the concentrations of individual trace elements are not reduced proportionately. Combustion of the washed coals resulted in increased concentrations of trace elements in the fly ash, although total fly ash loadings were reduced. Cleaning appeared to have little effect on concentrations of gaseous trace elements in the flue gas. The partitioning of the more volatile trace elements such as mercury and selenium between the vapour and solid phase was influenced by the amount of excess oxygen in the furnace, presumably affecting carbon-in-ash levels.The results suggest that the coal cleaning undertaken for these experiments did not significantly reduce the emissions to atmosphere of trace elements. The ultimate emissions will be determined by the efficiency of the dust capture systems.     

Principles of the production of valuable metal compounds from fossil fuels

The main methods for the production of potentially valuable elements from fossil fuels (petroleum and coal) are considered. A large body of factual data on this problem is analyzed based on the experimental and theoretical studies and the works of foreign and Russian scientists. The methods of the extraction of potentially valuable elements, in particular, Ge from coals and V from oils and petroleum products, are described. It is shown that, in addition to fossil fuels with the technological concentrations of potentially valuable elements, some by-products of the processing of caustobioliths are of interest for the recovery of these elements. These are mainly fly ashes, slags, and their mixtures trapped after the combustion or gasification of coals and oil conversion products and also after the utilization of overburden rocks and high-ash cleaning rejects by thermal methods. The minimum concentrations of a number of potentially valuable elements in fossil fuels are roughly estimated, at which oils and coals should be considered as complex raw materials for the use of their organic matter and the manufacture of the commercial compounds of valuable trace elements.     

Behaviour of elements and minerals during preparation and combustion of the Pernik coal,Bulgaria

The chemical and mineral composition, including major (Al, Ca, Fe, K, Mg, S, Si, Ti), minor (Na, P) and trace (Br, Cl, Co, Cr, Cu, Li, Mn, Ni, Pb, Rb, Sr, Zn) elements and different minerals, of the Pernik subbituminous coals and their preparation and combustion solid waste products were studied. Feed coals, upgraded coals (high-grade and low-grade coals) and their waste products, namely coal slimes and host rocks generated from the Pernik coal preparation plant, as well as combustion waste products such as bottom ashes, fly ashes and lagooned ashes resulted from the Republica coal-fired thermoelectric power station were characterized. The occurrence and behaviour (partitioning, volatilization, condensation, capture and retention) of the above-mentioned elements and various minerals during coal preparation and combustion are described. The results indicate some technological problems and possible environmental pollution of the air, water, soil and vegetation with certain elements in the areas surrounding both thermoelectric power station and coal preparation plant.     

Chemometric analysis of trace elements distribution in raw and thermally treated high sulphur coals

In the present study, chemometric analysis is applied as a tool to evaluate the release behaviour of trace elements (TEs) during coal utilization processes. Principal component analysis (PCA) and linear discriminant Analysis (LDA) were applied on the TE concentrations of raw and thermally treated coals. PCA and LDA successfully predicted the association of 21 trace elements (Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sb, Te, Pb) contained in coal and their thermal behavior at various temperatures. Application of chemometric on thermally treated coals shows that at temperature 450 °C, elements like Na, P, K, Fe, Ca, Mg, Al and Si have affinity with mineral matter and therefore have low volatility. Elements like Te, Sb and Ti may form their chlorides, which enhance the volatilities of these elements, while Co and Pb may form sulfides like Co₂S₄ and PbS. In the temperature range of 600-850 °C, either coal undergones an intense degradation of its structure during pyrolysis and the elements released may be adsorbed on coal surface or be volatile. The elements Cr, Co, V, Ni may react with sulphurous gases evolved during pyrolysis. At temperature 1000 °C, wide dispersion in data elements interact with carbon and sulphur compounds of coals. The formation of compounds like Si carbide, bassanite, gehlenite, anarthite may also be responsible for low volatilities of the elements Si, Al and Ca at higher temperatures. Predictive capabilities of PCA and LDA were evaluated in terms of TEs volatilities at different temperatures. The results of chemometric analysis are not only in good agreement with volatilities of TEs present in coals at various temperatures but also with FTIR analysis.     

Leaching of ashes and chars for examining transformations of trace elements during coal combustion and pyrolysis

One sub-bituminous coal and two bituminous coals were subjected to the combustion and pyrolysis by slow heating to a temperature ranging 550-1150 °C. Leaching of raw coals, ashes and chars with dilute HCl and HNO₃ was carried out, and leachate concentrations of major and trace elements were determined. Such a comparative leaching method was validated for characterizing the modes of occurrence of trace elements in coal and their transformations upon heating. Leaching results suggested that Be, V, Co, Cr and Ni were partially associated with organic matter, and As was partially associated with pyrite. During the ashing at 550-750 °C, the organically associated trace elements in coal formed some acid-soluble species. After the ashing at 1150 °C, Be, Co, Cr and Ni, together with Mn, Zn, and Pb, were immobilized in ash against leaching, whereas As was not immobilized. After pyrolysis, the organically associated trace elements in chars remained insoluble in both acids, and some HNO₃-soluble As in coal turned to a HNO₃-insoluble species.