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.     

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.     

Determination of elemental composition of cement powder by Spark Induced Breakdown Spectroscopy

Measurement of the cement powder composition as a major building material is considered very important. In this paper the capabilities of Spark Induced Breakdown Spectroscopy (SIBS) as a new technique for analysis of cement powder are shown. The major and minor elements of cement such as Ca, Si, Fe, K, Mg, Al, Na, Ba, Ti, V, Pb, Mn and Sr are detected qualitatively. For quantitative measurement, calibration curves are prepared for elements Ca, Si, Mg, Al, Fe and K with limit of detection below 220 ppm. The critical problems such as how to achieve quantitative measurement and improve the detection limits are investigated. The potential and drawbacks of SIBS technique in comparison with XRF for analysis of powder products are discussed.     

Production of ultra clean coal: Part III. Effect of coal's carbonaceous matrix on the dissolution of mineral matter using hydrofluoric acid

An Australian bituminous coal was treated with increasing concentrations of hydrofluoric acid (HF), and the extraction levels of Al, Si, Fe, Ti, K, Na, Ca and Mg were determined. These extraction levels were compared to those obtained when the mineral matter alone, produced by ashing the coal at a low temperature, was treated with HF, in order to quantify the extent that the carbonaceous matrix inhibits extraction. The carbonaceous matrix inhibits the dissolution of Ti to a large extent. Si and Fe are the next most inhibited elements. It is proposed that the Ti is present as extremely small particles, of possibly less than 1 μm in length, which are finely disseminated throughout the coal.     

中低温煤焦油蒸馏过程中金属元素的迁移规律

以中低温煤焦油轻油和重油为实验原料,采用常压蒸馏获得170~200℃、200~240℃、240~270℃、270~300℃、300~320℃、320~340℃、340~360℃和360~390℃煤焦油馏分油;利用配有油品加氧制冷进样系统的ICP-OES测定了21种微量元素在馏分油中的含量,考察了不同馏分油中元素的分布情况。研究表明：在原煤焦油中,未发现Ag、Mg、Mo、Na、Ni、Fe、Mn、Cr及Ti元素,含量较高的元素有Sn、P、Al、Pb、Si,其中Sn元素在轻油和重油中的含量分别为11.78μg/g和14.04μg/g;在所有馏分油中,未发现Al、Mo、Fe、Mn、Cr及Ti元素,含量比较高的元素有Si、Sn、Na、Zn、Pb,特别是Si、Na、Sn、Zn、Ni、Pb及B元素可以有效富集于馏分油中。可能的原因是Ca、Fe、Mg、Al等金属以不同的盐类形态存在,在煤焦油脱水及<170℃蒸馏过程中,这些金属盐类会被部分带出,导致其在馏分油中的含量未富集或未检出;通过关联金属元素在馏分油中的分布与其组成的关系,馏分油中元素的分布可能与酚类化合物、杂环化合物和蒸馏温度等相关。酚类化合物及杂环化合物可能与Ag、B、Cu、Mo、Sn、Na、Zn、Ca、Pb等金属形成络合物或卟啉配合物,蒸馏温度一方面可以破坏Sn、Cd、Pb、Zn、Cu、Ca、Pb等元素在馏分油中的结合力,另一方面也可以促进这些元素与馏分油中的含氧、含氮等化合物更好地发生化合反应,进而影响金属元素在馏分油中的含量分布。     

Generation of ultra-clean coal from Victorian brown coal — Sequential and single leaching at room temperature to elucidate the elution of individual inorganic elements

This paper addressed the probability of the generation of ultra-clean coal from chemical leaching of low-rank Victorian brown coal. Sequential leaching was employed to determine the modes of occurrence of the major elements in the two coals studied, including Na, K, Mg, Ca, Fe, Al, Ti, and Si. The results indicate that, the modes of occurrence of individual metals vary greatly with brown coal sample and elemental type. For one brown coal tested, it is dominated by water-soluble and ammonium acetate-soluble ion-exchangeable cations. Therefore, a single washing through the use of woody biomass-derived pyroligneous acid or citric acid easily reduced the concentrations of its overall ash and even sulphur and chlorine to meet the requirements for gas turbine fuel. The leaching of the organically bound cations in this coal was also very rapid and completed in 5 min. In contrast, another brown coal tested is mainly composed of quartz and/or clay compounds which remained intact even after being leached with 5 M nitric acid. These mineral grains possess two peak size ranges in the coal, 1.0-2.2 μm and 4.6-10 μm. The former size bin was embedded deeply in coal matrix, and hence, its leaching upon acids was very slow when compared with coarse particles which are mostly discrete grains residing separately from coal matrix. The Na-EDTA was found to be able to mobilise the small grains substantially through its Na ion to penetrate coal matrix to react with Al, forming acid-soluble Na aluminates. The ammonium acetate-insoluble Ti and Fe polyhedra were also mobilised by the EDTA. Accordingly, the overall ash content in coal residue accounts for ~ 1.5 wt.%, relative to 2.6 wt.% in the corresponding raw coal and 2.0 wt.% in the ammonium acetate-insoluble residue.     

The fate of trace elements and bulk minerals in pulverized coal combustion in a power station

The behaviour of 15 trace elements (As, Ba, Cr, Cu, Mn, Mo, Nb, Ni, Pb, Rb, Sr, V, Y, Zn and Zr) and 10 major and minor elements (Al, Ca, Fe, K, Mg, Na, P, S, Si and Ti) in coal during combustion in a power station has been studied. Synchronized sampling of pulverized coal, bottom ash and fly ash was undertaken over a limited time period. Fly ash morphology was studied by SEM and the mineral composition was studied by EDX and XRD. Major, minor and trace elements were determined by XRF and AAS. Differences between the composition of the ashes of pulverized coal, bottom ashes and fly ashes have been observed. As, Cu, Mo, Pb and Zn were concentrated in the fly ash. The relationship between the composition of the fly ashes and their particle size was studied. Enrichment factors were calculated for each element in different size fractions. As the particle sizes of fly ash decrease, the concentrations of As, Cu, Mo, Pb and Zn increase. From the different composition of bottom ashes and fly ashes (and relying on the results of the characterization of the feed coal carried out in previous work), it can be assumed that pyrite and carbonates make a greater contribution to the furnace bottom ashes. Quartz carries through into the fly ash. This mineral is almost absent in the finest fractions, reflecting the absence of small quartz particles in the feed coal.     

微波消解-ICP-OES法测定黑芝麻中的18种矿质元素

采用HNO3/H2O2湿法微波消解制样,利用全谱直读电感耦合等离子原子发射光谱法(ICP-OES),全面详细地分析测定了黑芝麻中的矿质元素,共检出Ca、P、S、Mg、K、Al、Si、Fe、Na、Zn、Se、Sr、Cu、Mn、Ba、B、Ti、Cr等18种矿质元素,RSD值在1.21%～10.1%,其中13种元素在5%以内。黑芝麻中所含人体常量元素Ca、P、S、Mg、K、Na等的质量分数分别为1.79%,1.08%,0.59%,0.43%,0.41%和0.009 1%;微量元素Fe、Zn、Se、Cu、Mn、B、Cr、Sr、Si、Al等的含量分别为18.6,4.55,3.87,1.74,1.62,0.91,3.21,78.8,125.8 mg/100 g,未检出Pb、Hg、Cd、As以及Ni、Co、Mo等元素。     

Multi-element determinations of N,N-dimethylformamide (DMF) coal slurries using ICP-OES

A slurry nebulisation technique was applied for elemental analysis of bituminous coals SARM 18, SARM 19 and four coals from three different seams in Witbank, South Africa, by inductively coupled plasma optical emission spectroscopy (ICP-OES). Major elements (Al, Ca, Fe, Mg, S, Si and Ti) and trace elements (Ba, Cr, Mn, Ni, Sr, V, Zn and Zr) in coal were determined. Various slurry preparations were evaluated using two dispersants (glycerol and Triton X-100) and by varying the concentration of dispersants, between 0.1% and 1.0% (v/v). The effect of initially solubilising the ground coal in N,N-dimethylformamide (DMF) was investigated by varying the volume of DMF added. The effect of wet grinding with DMF was investigated. Wet grinding with DMF was shown to drastically reduce particle sizes (50.0% < 0.28 μm and 90.0% < 6.17 μm) as compared to dry grinding (50.0% < 5.25 μm and 90.0% < 11.1 μm). The reduced particle sizes and increased transport efficiency of the coal slurries led to improved analytical recoveries of elements in the reference coal, SARM 18. The best analytical recoveries for all elements were achieved using 0.1% Triton X-100 with 10.0% DMF. Results obtained by ICP-OES after wet grinding of the coal with DMF, using 0.1% Triton X-100, also gave excellent recoveries (Al, 100%; Ca, 103%; Cr, 106%; Fe, 102%; Mg, 100%; Mn, 104%; Ni, 109%; Si, 102%; Ti, 95.0%; and V, 108%). The results obtained with 10.0% DMF and 0.1% Triton X-100 were in agreement with certified values for all selected elements according to paired t-test at the 95.0% confidence level. Selected elements (Al, Ca, Fe, Mg, Mn, Si, Ti and V) were also analysed with X-ray fluorescence for comparison with results obtained from ICP-OES. Analysis by ICP-OES of microwave digested coal was also carried out. It is suggested that the DMF slurry technique could be used for routine analysis of bituminous coals.     

Effect of rank,temperatures and inherent minerals on nitrogen emissions during coal pyrolysis in a fixed bed reactor

Pyrolysis of 11 coals with carbon contents of 77–93 wt.% (daf) and corresponding demineralized samples has been studied in a fixed bed quartz reactor with a heating rate of 20 K/min to examine rank, demineralization, temperature and inherent mineral species dependences of nitrogen distribution. Nitrogen mass balances fall within 92.5–104.6%. The results indicate that the chars derived from the coals with higher rank show larger nitrogen retention. Demineralization suppresses volatile nitrogen emission during coal pyrolysis, especially for low rank coals. Coal-N conversion to tar-N reaches the asymptotic values at 600 °C. HCN yields are lower than NH₃ yields during coal pyrolysis. The trends in HCN and NH₃ emissions are very similar and the yields reach the asymptotic value at about 1200 °C. N₂ starts emitting at 600 °C, and as the temperature increases the conversion increases linearly with a corresponding reverse change of char-N. With the catalysts added, N₂ formation is prompted with the sequence of Fe>Ca>K>Ti≫Na≫Si≈Al, meanwhile, char-N decreases correspondingly. Fe, Ca, K, Na, Si and Al increase coal-N conversion to NH₃ with the sequence of Fe>Ca>K≈Na≫Si≈Al in the pyrolysis. Na addition prompts HCN formation; however, the presence of Ti and Ca decrease the HCN yields with small value. The other catalysts have no notable influence on HCN emission in the pyrolysis. Demineralization and Ti addition increase coal-N conversion to tar-N slightly whereas K, Ca, Mg, Na, Si and Al additions decrease tar-N yield weakly, other catalysts hardly influence tar nitrogen emission. N₂ emits mainly from char-N with slight contribution of volatile nitrogen. The mechanism of different N-containing species formation and catalysts influence in the pyrolysis is also discussed in the paper.     

微波消解-ICP-OES法测定肉苁蓉中矿质元素

经HNO3/H2O2湿法微波消解制样,利用全谱直读电感耦合等离子原子发射光谱法(ICP-OES),测定了青藏高原地区产肉苁蓉中的矿质元素。结果显示,肉苁蓉中含有Na、K、Ca、P、S、Mg、Si、Al、Fe、Li、Ti、Sr、Mn、Zn、Cu、Ba、B、Cr等18种矿质元素。测定结果相对标准偏差RSD值在0.85%～12.6%,其中14种在5%以内。常量元素中,Na、K、Ca、P、S、Mg的质量分数分别为4.03%,1.23%,0.31%,0.32%,0.29%,0.17%;微量元素中,Fe、Mn、Zn、Cu、Cr含量分别为788.3,16.87,15.29,7.18,1.24 mg/kg。     

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.     

660MW燃煤锅炉细微颗粒物中次量与痕量元素的分布特性

应用承重撞击器(DGI)采样系统在南昌某电厂2^#锅炉电除尘器前进行颗粒物采集,并同时采集了原煤样和底灰样。对飞灰的质量粒径分布、底灰和飞灰中次量与痕量元素的分布特性进行了分析。结果表明PM_1.0和PM_2.5质量分别占PM₁₀质量的16.0%~17.4%和46.9%~50.6%;Na、Mg、P、S主要富集在亚微米颗粒物中,Al、Si、Ca、Ti、Fe、K主要富集在超微米颗粒物中;随着颗粒物粒径的减小,As、Cd、Cr、Pb的浓度逐渐增大,且在亚微米颗粒物中的增幅大于超微米颗粒物,Mn在各级颗粒物中浓度相近;As、Cd、Cr、Pb大量富集于亚微米颗粒物之上,Mn在各级颗粒物中富集特性无明显差异,且各痕量元素挥发特性存在以下规律:As>Cd>Cr>Pb>Mn;文中给出了无控制条件下痕量元素的排放因子,PM_1.0中各元素排放比例存在以下规律:As>Cd>Cr>Pb>Mn。     

藏雪莲水母雪兔子中矿质元素的测定与分析

经HNO3/H2 O2湿法微波消解制样,利用全谱直读电感耦合等离子原子发射光谱法(ICP-OES),分析测定了青藏高原地区产藏雪莲水母雪兔子中的矿质元素.结果显示,藏雪莲水母雪兔子中含有K、Ca、P、Mg、Al、S、Fe、Si、Na、Mn、Ti、Sr、Ba、B、Zn、Cu、Cr等17种矿质元素,定量分析结果相对标准偏差...     

煤粉炉掺烧生活垃圾对灰渣特性的影响研究

利用小试规模煤粉炉,研究掺烧不同比例生活垃圾对燃煤灰渣特性的影响,主要包括飞灰元素组成、飞灰粒径分布、飞灰形貌、灰熔点和结渣特性等影响变化研究。结果表明,随着生活垃圾掺烧比例的增加,灰分中Ca、Fe、Cl和S元素含量增加,Al、Mg、K、Na、Ti和Si含量降低,飞灰球形颗粒分布减少,层状堆积结构增多;灰渣熔融特征温度呈平缓下降趋势,但变化范围小于2%,影响较小;掺烧量为25%时,飞灰表面发现少量褐色大颗粒。总之,生活垃圾掺烧对燃煤灰渣特性影响很小,该结果为实际煤粉炉开展掺烧生活垃圾试验提供了一定理论基础。     

Metal recovery from coal ash via chlorination — A thermodynamic study

Coal ash can become an important mineral substitute for the recovery of several metals, especially aluminum and titanium. A plausible route for the recovery could be via high temperature chlorination in the presence of a reducing agent. The thermodynamics of the reaction system for the free energy computations consisted of 135 chemical species containing 12 elements, namely Al, C, Ca, CI, Fe, K, Mg, Na, O, S, Si and Ti. The results indicate that the chlorination route is feasible over a wide temperature range.     

ICP-AES测定以硅酸盐为主的矿物中Al、Fe、Ca、Mg、K、Na、Ti、Mn等元素的方法

研究了应用电感耦合等离子体发射光谱法 ,选取适宜的仪器工作条件 ,分析硅酸盐矿样中Al、K、Na、Ca、Mg、Ti、Mn、Fe8个元素的方法。与传统方法相比 ,大大简化了操作程序和劳动强度 ,缩短了工作时间。用本法对岩石系列标准物质中 8个元素进行了分析 ,其结果与参值相符。     

Thermodynamic simulation of the composition of mineral compounds upon the gasification of brown coal from the Kansk-Achinsk Basin

The quantitative composition of the products of the gasification (at P = 0.1 MPa and an air excess ratio of 0.3 in a temperature range of 114–1534°C) of brown coal from the Nazarovskoe deposit of the Kansk-Achinsk Basin was calculated using a chemical thermodynamics program [1], the database of which contains the thermodynamic constants of more than 2000 inorganic compounds. The calculation covered the compounds of both trace elements (V, U, Se, Sr, Ag, and Au) and ash-forming elements (Al, Si, Fe, Ca, Mg, K, Na, and S).     

茶花蜂花粉中常量、微量元素的分析测定

采用HNO3/H2O2湿法微波消解制样,利用全谱直读电感耦合等离子原子发射光谱法（ICP-OES）,全面详细地分析测定了茶花蜂花粉中的常量元素和微量元素,共检出16种。分析结果RSD值在0.45%~7.14%之间。茶花蜂花粉中所含P、S、K、Mg、Ca、Na等常量元素的质量分数分别为0.77%、0.73%、0.52%、0.13%、0.099%、0.010%;微量元素Mn、Si、Al、Fe、Zn、Cu、B、Ba、Sr、Ti等的含量分别为508.6、313.2、148.5、74.8、38.8、10.5、8.3、7.2、1.8、0.98 mg/kg。     

微波消解-ICP-OES法测定胡萝卜中19种矿质元素

利用HNO3/H2O2湿法微波消解制样、再应用全谱直读电感耦合等离子体原子发射光谱法(ICP-OES),对胡萝卜中的矿物元素组成进行全面的分析与测定。定量分析了K、Ca、P、Na、S、Mg、Al、Si、Ba、Zn、Fe、Sr、B、Cu、Mn、V、Pb、Cr、Ti等19种矿物元素,定量结果相对标准偏差在0.15%~10.3%之间,标准样品回收率测定在89.0%~109.6%之间。实验结果可为胡萝卜的应用研究提供基础数据。