The effect of anionic dispersants on grindability of different rank coals

The effect of PSS (Sodium Polystyrene Sulphonate) and NSF (Naphthalene Sulphonate Formaldehyde Condensate) chemicals used to control the pulp rheology on the grindability of coals was studied. Zonguldak region bituminous coal and Istanbul region brown coal samples that high and low rank were used. Wet grinding tests with two coal samples were performed with or without PSS and NSF under constant grinding conditions: solid ratios ranged from 50% to 60% with 0–60 min grinding periods.In the present study, grinding conditions of coal with high pulp solid ratio were improved through the lowering of the viscosity of the coal by using the dispersing agents, PSS and NSF, during the grinding stage and evaluation were made by using the “efficiency factor”. It is possible to increase the amount of finely ground bituminous coal from Zonguldak by 20% and 16%, if optimum concentrations of PSS (0.3%) and NSF (0.7%) are used, respectively. Whereas, the increase in the case of finely ground lignite from Istanbul was 32% and 20%, respectively.     

ScCO2-H2O作用下不同煤级煤化学结构变化的实验研究

超临界二氧化碳（ScCO₂）–H₂O–煤地球化学反应可造成煤物理结构和化学结构的改变,对煤层注CO₂增采甲烷的有效性尤为关键。为了探讨ScCO₂-H₂O-煤反应对不同变质程度煤化学结构的影响,选择3个不同煤化程度煤样,在自主研制的ScCO₂-H₂O-煤地球化学反应模拟实验装置中模拟1000m埋深条件下煤样与ScCO₂和去离子水反应240h,并对反应前后的煤样分别进行了X射线衍射和拉曼光谱实验,对比分析了反应前后煤样晶体结构和碳有序度的变化特征。测试结果表明：ScCO₂-H₂O反应破坏了煤的晶体完整性和碳有序度,改变了煤的大分子结构,且对低阶煤和中–高阶煤具有不同的影响,反应提高了低阶煤的平行定向程度,使其结构更加紧凑,减小了面网间距,而使中–高阶煤中无序单元增加,面网间距增大。该研究结果为CO₂-ECBM项目实施中ScCO₂-H₂O作用对煤储层吸附解吸特征和孔渗特征影响的研究奠定了微观尺度基础。     

我国不同时代不同煤级煤的吸附特征

通过对采自不同地区,各种煤级近500个煤样平衡水分条件下的等温吸附实验数据的统计分析,研究了我国主要成煤时代、煤级和平衡水分煤的吸附特征,以及其Langmuir体积和Langmuir压力的变化规律,分析了Langmuir常数与煤岩显微组分、矿物质含量、孔隙度的关系,探讨了煤的吸附机理及各因素对煤吸附能力影响的内在原因.     

Interactions between organic matter and minerals in two bituminous coals of different rank

The association between specific mineral and organic constituents in two Asturian bituminous coals of different rank was studied. For this, raw coals were fractionated by density and the variation of a number of parameters was followed in parallel. Results of coal chemical analyses, including analyses for 22 elements, were used to establish the elemental association with coal organic matter. Petrographic analyses determined the distribution of macerals among densimetric fractions, vitrinite reflectance being at a minimum in the intermediate density fractions. Mineral species were identified by X-ray diffraction, FT-IR spectroscopy and Mössbauer spectroscopy. Comparison of trends for different parameters determined using this set of techniques allowed classification of the various minerals according to their association with organic matter. Carbonates seem to be specifically associated with the organic matter of the low-volatile bituminous coal whereas sulfides concentrate in the organic matter of the high-volatile bituminous coal. Vitrinite is the maceral exhibiting the most probable association with inorganic matter. The possibility of a merely physical association of fine-grained detrital minerals with organic matter cannot be excluded; nevertheless, one must bear in mind that even this type of interaction is important due to its effect on various coal preparation and utilization processes.     

邯郸-峰峰矿区不同变质程度煤中有机氮的赋存形态

氮是煤中的常见元素之一,煤中氮的赋存形态多样且随煤阶发生变化。以邯郸-峰峰矿区为例,利用X射线光电子能谱（XPS）实验,研究不同变质程度煤（R_ran=1.08%~3.67%）中有机氮的赋存形态,探讨煤中各形态有机氮相对含量随煤阶的变化规律。结果表明：按N 1s XPS谱图分峰峰值的结合能可将煤中氮的形态归为N-6、N-5、N-Q和N-X四种;研究区煤中N-5的相对含量最高,且随着煤阶的增高而降低;N-Q的相对含量随着煤阶的增高而增高;煤中N-6的相对含量随煤阶呈“增-减-稳”的变化规律;N-X的相对含量为9.1%~35.1%,其与煤阶关系不明显;在煤阶R_ran=1.08%~1.47%的范围内,煤的N 1s XPS谱图中缺失N-Q分峰,表明褐煤中相对含量最高的质子化吡啶氮在此阶段已几乎全部去质子化而转化为吡啶氮。不同变质阶段氮的赋存形态变化特征对燃煤发电及煤化工领域煤化学参数选取提供参考。     

The joint effect of rank and grain size on the flotation of Australian bituminous coals

Laboratory batch flotation tests were carried out to determine the effect of grain size on the recovery of four Australian bituminous coals of high and low rank. The flotation concentrates, taken over successive time intervals, and the tailings, were sized and the recovery-size curves plotted. A method was developed for determining the proportions of liberated and composite grains in the various flotation products. Flotation tests were carried out in the presence of methylisobutylcarbinol (MIBC) and MIBC + kerosene. The shapes of the recovery-size curves depended on the rank of the coal and whether or not kerosene was present. The variation of the recovery with size was explained in terms of the joint effect of rank and size on the floatability of composite grains.     

Correlation between optical, chemical and micro-structural parameters of high-rank coals and graphite

In order to identify the parameters that best characterize the chemical and structural evolution of organic matter during coalification, the relationships between optical, chemical and micro-structural parameters in high-rank coals and natural graphite were studied. The samples include anthracites from Peñarroya–Belmez–Espiel Basin (Spain), Douro Basin (Portugal), and Alto Chicama Basin (Peru); and natural graphite from Canada, Mozambique, and Austria.Correlations between the following optical parameters were assessed: vitrinite random reflectance (R_r), Reflectance Indicating Surfaces (RIS) axis (R_MAX, R_INT and R_MIN), and RIS parameters (R_am, R_ev and R_st), as well as B_w and AI anisotropy parameters. Furthermore, the chemical parameters used were chosen according to their significant variation in coals, namely volatile matter, carbon, and hydrogen contents calculated in dry ash free basis (VM_daf, C_daf, H_daf), as well as the H/C atomic ratio. Structural organization was characterized by micro-Raman spectroscopy and XRD. Raman parameters used were the full width at half maximum (FWHM) and position of G and D1 bands on the first-order Raman spectrum, and the ID1/IG intensity area ratio. The selected XRD parameters were interlayer spacing d₀₀₂, and crystallite sizes L_a and L_c.Results show that: (i) R_MAX RIS axis seems to correlate best with chemical and micro-structural parameters; (ii) for the majority of studied samples, H_daf and H/C atomic ratio are the only chemical parameters with significant correlations with R_MAX; (iii) the FWHM of the G band of Raman spectrum shows good linear correlation with the XRD parameter d₀₀₂; and, (iv) structural organization of carbon materials, as measured by trends in their optical and crystalline parameters, is influenced by their hydrogen content (daf basis) and therefore by the H/C atomic ratio.     

北淮阳地区不同变形-变质煤的元素分布及其影响因素

通过对大别造山带前陆北淮阳地区石炭纪高煤级煤的X射线荧光光谱分析,探讨了不同变形-变质类型煤中常量元素的分布规律及其影响因素。结果表明:构造-热作用具有使Al³⁺、K⁺、Si⁴⁺、Ti⁴⁺在煤体中富集,P⁵⁺、Fe²⁺+Fe³⁺、Mn²⁺Na⁺、Ca²⁺、Mg²⁺向煤体外迁移的趋势;在弱应力带富集Al³⁺、K⁺、Ti⁴⁺、Na⁺、Ca²⁺;在强应力带富集Si⁴⁺、P⁵⁺、Fe²⁺+Fe³⁺、Mg²⁺。岩浆热变质类型煤和构造-热变质类型煤的w(SiO₂)/w(Al₂O₃)和w(K₂O)/w(Na₂O)值显著增大,与岩浆岩中SiO₂及K₂O质量分数偏高有重要的成因联系。     

Gondwana coals of Bhutan Himalaya - Occurrence,properties and petrographic characteristics

A narrow belt of highly inclined coal-bearing Gondwana strata occurs in the extreme south-eastern part of Bhutan Himalaya. Recently, a systematic survey was undertaken along this coal belt and coals of three areas were analyzed in detail for the evaluation of their physico-chemical properties and petrographic characteristics.The entire region is in the midst of the Great Himalayan orogenic belt, and the whole stratigraphic sequence underwent several diastrophic movements in the geological past. The massive effects of these orogenies is more pronounced in the coal beds of Gondwana sequence, and due to severe crushing and tectonic shearing these coals became powdery and flaky in nature. Significantly, the coals retained their pre-deformational rank exhibiting typical high-volatile, low-rank, bituminous characters, with mild caking propensities. Also these coals are markedly low in sulphur, phosphorus, chlorine and carbonate content like that of Peninsular Gondwana coals.Petrographic studies of these Bhutan coals revealed a close similarity with the eastern Raniganj coals (Upper Permian) of Peninsular India. The tectonic shearing and crushing of the coals are exhibited by the frequent presence of microfolding, microfaulting, and other compressional structures. However, the coals of all the three areas have shown a consistently low order of reflectance values.This typical retention of pre-deformational low-rank bituminous character is a significant feature of Bhutan coals. It shows that massive orogenic movements were only able to physically crush these coals but could not generate the requisite thermal regime to raise the rank of these coals.     

基于HYDRUS模拟的ABCD模型变量及参数物理基础研究

以ABCD模型为代表的概念性水文模型是量化水文循环过程的主要手段之一,但是很少有研究检验ABCD模型变量和参数的物理基础及其与传统土壤水力参数的关系。以鄂尔多斯盆地台格庙矿区作为研究区,首先使用HYDRUS-1D软件构建站点尺度土壤-植物-大气连续体模型模拟获取非冻结期“真实的”实际蒸散量,其作为目标函数对ABCD模型进行校正,然后对比ABCD模型模拟的土壤水储量和土壤水渗漏量与SPAC模型模拟的结果,通过开展大量情景模拟探究ABCD模型中关键参数a和b与传统土壤水力参数之间的关系。结果表明：在站点尺度,ABCD模型可以用于模拟非冻结期月时间尺度的实际蒸散量和土壤水渗漏量;ABCD模型中参数a与饱和含水率、残余含水率和曲线形状参数具有较强的线性相关性,与饱和渗透系数呈对数关系;参数b与饱和含水率和曲线形状参数n具有较强的线性相关性,与饱和渗透系数和曲线形状参数α呈对数关系。研究结果可以提高对概念性水文模型变量和参数物理基础的认识,拓展水文模型在水文地质中的应用。     

The microconstituents of Godavari coals,South India

The present paper deals in detail with the coal typology, rank and correlation of some Indian coal seams. Petrological evaluation of several known coal seams reveals that there are two main seams, the King (lower) seam and Queen (upper) seam, with distinctly different characteristics. All the other seams, locally known by different names elsewhere in the field, are correlatable with either the King or Queen seams.The coals are of inferior quality because of the predominance of mixed coals types associated with dispersed mineral matter. However, some seams show characteristics which are amenable to quality improvement with suitable preparation methods. The coals appear to have been formed rapidly in a fluctuating environment (aerobic to anaerobic) under relatively cold to gradually warming conditions.     

Mineralogy and geochemistry of different morphological pyrite in Late Permian coals,South China

The mineralogical and morphological characteristics, concentration of major and trace elements, and sulfur isotopic composition of three pyrite and two coal samples in the Upper Permian high-sulfur coals from Xingren, Zhijin, and Hefeng mining area, South China, were investigated, by using optical microscopy, field emission-scanning electron microscopy in conjunction with an energy-dispersive X-ray spectrometer (FE SEM-EDS), X-ray powder diffraction (XRD), X-ray fluorescence (XRF), inductively coupled plasma mass spectrometry (ICP-MS), cold vapor atomic absorption spectrometry (CVAAS), and isotopic ratio mass spectrometer. The pyrite in Xingren and Zhijin coals mainly occurs as nodular, lens-shaped, thin-layer, and massive forms, and it occurs mainly as fine vein fillings in the Hefeng coals. Microscopically, pyrite in the coals from Xingren, Zhijin, and Hefeng mainly occurs as framboidal, cell-filling, and vein-filling forms, respectively. There is a distinct difference in X-ray powder diffractogram and diffraction data of the three pyrite samples. There is a maximum diffraction peak (2.709 Å) in pyrite in the coals from Xingren and (2.707 Å) in pyrite in the coals from Zhijin; however, the maximum diffraction peak is 3.343 Å in pyrite in the coals from Hefeng. The average unit cell length (a ₀) is 5.4169 Å for the Xingren pyrite, 5.4159 Å for the Zhijin pyrite, and 5.4170 Å for the Hefeng pyrite. The ratio of S/Fe is 2.16 for the Xingren pyrite, 2.09 for the Zhijin pyrite, and 2.01 for the Hefeng pyrite. Copper (701 μg/g), Ni (369 μg/g), and Co (29.6 μg/g) concentrated in the Hefeng pyrite. The concentration of As is 126, 19.6, and 19.1 μg/g in the Hefeng, Zhijin, and Xingren pyrite, respectively. Mercury is 11.7 μg/g in the Xingren pyrite, 2.79 μg/g in the Zhijin pyrite, and 0.512 μg/g in the Hefeng pyrite. There is a clear tendency that elements Cu, Ni, Co, Cr, Se, Mo, and As are significantly enriched in the Hefeng pyrite. Mercury is greatly enriched in the Xingren pyrite, and Zn is enriched in Zhijin pyrite. Rare earth elements and yttrium (REY) are not abundant (8.276 μg/g) in the Hefeng pyrite and are characterized by maximum positive anomaly of Eu (Eu/Eu* = 6.54). The δ³⁴S value is ?26.9 ‰ in the Xingren pyrite, +3.8 ‰ in the Zhijin pyrite, and +3.7 ‰ in the Hefeng pyrite. The trace elements in the Hefeng pyrite and coal are As (126 and 6.1 μg/g), Hg (0.512 and 0.158 μg/g), Zn (276 and 56.7 μg/g), Se (16.5 and 1.07 μg/g), Mo (45.5 and 9.93 μg/g), Cu (701 and 37.8 μg/g), Ni (369 and 16.9 μg/g), Co (29.6 and 8.63 μg/g), Sb (2.64 and 0.742 μg/g), Cd (3.49 and 0.366 μg/g), and Pb (62.8 and 33.5 μg/g), demonstrating that these potentially toxic trace elements were mainly concentrated in pyrites. The strongly positive Eu anomaly (Eu/Eu* = 6.54) in the netted pyrite vein filled in the cleats of the Hefeng coal may be the product of epigenetic hydrothermal fluid.     

Anthracitization of coals in the South Wales coalfield

Investigations by the Institute of Geological Sciences on potential geothermal water sites in the coalfield of South Wales have been reported. They are of considerable interest and revive the controversy about the nature of the heat-source responsible for the anthracitization of some coals in this classic area. In the absence of exposed post-Carboniferous igneous rocks in the coalfield, general opinion has favoured heat generation by friction along faults or “disturbances”. We re-examine the evidence in the light of more recent geophysical and geochemical investigations which suggest the possibility of igneous intrusions at a depth of about 3.5 km or shallower. The likely age of such intrusions is also considered. High seismic velocity basement rocks rise to only 2.5 km beneath the surface of the Carboniferous in the northwestern anthracitized zone of the coalfield and we suggest that anthracitization in South Wales is not the result of depth of burial nor of frictional heat but of proximity to a magmatic heat source associated with crystalline rocks of the basement.     

Correlation of yields of pyrolysis products and rank of Styrian lignites and subbituminous coals

Ulminites (telocollinites) from Styrian coal-bearing formations (southeastern Austria) ranking from diluvial lignites upto subbituminous coal of Carpathian age were investigated. Characterization by means of infrared spectroscopy, pyrolysis-gas-chromatography and reflectance measurements was done. A statistical analysis showed a strong correlation between the mean reflectance of ulminite and certain products of pyrolysis, i.e. the ratio of the amounts of toluene and benzene. On the other hand, no correlations could be established between the data obtained from infrared spectroscopy of the undecomposed samples and the data from the other experimental methods mentioned above. The pyrolysis-chromatography-technique can be applied quickly and easily to a large number of samples requiring only a few milligrams of material.     

Role of coal type and rank on methane sorption characteristics of Bowen Basin, Australia coals

The effect of coal composition, particularly the organic fraction, upon gas sorption has been investigated for Bowen Basin and Sydney Basin, Australia coals. Maceral composition influences on gas retention and release were investigated using isorank pairs of hand-picked bright and dull coal in the rank range of high volatile bituminous (0.78% R_{o max}) to anthracite (3.01% R_{o max}). Adsorption isotherm results of dry coals indicated that Langmuir volume (V_L) for bright and dull coal types followed discrete, second-order polynomial trends with increasing rank. Bright coals had a minimum V_L at 1.72% R_{o max} and dull coals had a minimum V_L at 1.17% R_{o max}. At low rank, V_L was greater in bright coal by about 10 cm³/g, but as rank increased, the bright and dull trends converged and crossed at 1.65% R_{o max}. At ranks higher than 1.65% R_{o max}, both bright and dull coals followed similar trends. These competing trends mean that the importance of maceral composition on V_L varies according to rank. In high volatile bituminous coals, increases in vitrinite content are associated with increases in adsorption capacity. At ranks higher than medium to low volatile bituminous, changes in maceral composition may exert relatively little influence on adsorption capacity. The Langmuir pressure (P_L) showed a strong relationship of decreasing P_L with increasing rank, which was not related to coal type. It is suggested that the observed trend is related to a decrease in the heterogeneity of the pore surfaces, and subsequent increased coverage by the adsorbate, as coal rank increases. Desorption rate studies on crushed samples show that dull coals desorb more rapidly than bright coals and that desorption rate is also a function of rank. Coals of lower rank have higher effective diffusivities. Mineral matter was found to have no influence on desorption rate of these finely crushed samples. The evolution of the coal pore structure with changing rank is implicated in diffusion rate differences.     

A study of the kinetic parameters of individual macerals from Upper Permian coals in South China via open-system pyrolysis

A unique Upper Permian coal, Leping coal, is widely distributed in South China. The coal samples studied in the paper were collected from two mines in the Shuicheng coalfield of Guizhou Province, southwest China. The geochemical works including coal petrography, maceral content, Rock–Eval pyrolysis, and kinetic modelling of hydrocarbon-generating have been carried out on whole coal and individual macerals. The higher contents of volatile matter, elemental hydrogen, and tar yield, and the high hydrocarbon generation potential of the Leping coals are attributed to their high content of “barkinite”, a special liptinite maceral.The hydrocarbon generation potential of “barkinite” (S₂=287 mg/g, hydrogen index (HI)=491 mg/g TOC) is greater than that of vitrinite (S₂=180 mg/g, HI=249 mg/g TOC), and much higher than that of fusinite (S₂=24 mg/g, HI=35 mg/g TOC). At the same experimental conditions, “barkinite” has a higher threshold and a narrower “oil window” than those of vitrinite and fusinite, and consequently, can generate more hydrocarbons in higher coalification temperature and shorter geological duration. Data from the activation energy distributions indicate that “barkinite” has a more homogenous chemical structure than that of vitrinite and fusinite. The above-mentioned characteristics are extremely important for exploring hydrocarbon derived from the Leping coals in South China.     

Mercury-binding forms in coals and their geological provenances in coals of different types

Mercury (Hg) is an element of environmental and geological significance. Quantification of different Hg-binding forms is crucial to understand geological Hg provenances and associated geochemical processes during coal formation. In this study, seven coal samples were selected, according to coal rank (i.e., middle volatile bituminous, C-3; low volatile bituminous, C-2; anthracite, C-1), chemical anomalies (high S coal, IBC-105; high Cl coal, C22650) and sampling environment (fresh coal, LH; weathered coal LHW), to determine their Hg-binding forms using well-established sequential extraction procedures coupled with sink–float experiment. In the thermally metamorphosed samples C-1 and C-2, a comparative enrichment of total Hg relative to C-3 is observed. Silicate- and organic-bound Hg are the dominant Hg-binding forms in C-1, suggesting possible Hg sources from magma silicate and secondary Hg enrichment by adsorption. Sulfide- and organic-bound Hg are the most abundant Hg-binding forms in IBC-105, whereas only organic-bound Hg dominates in CC22650. Weathering processes are suggested to transform the abundant sulfide-bound Hg in LH to silicate- and organic-bound Hg in its weathering product LHW.     

The relationship between macerals and sulphur content of some South African Permian coals

There is a positive correlation between sulphur concentration and the vitrinite maceral group content in Permian Vryheid Formation coals in South Africa; the reverse is true for the inertinite maceral family. This relationship is evident at intraseam, interseam and intercoalfied levels. Vitrinite precursors formed where the water table in peat-forming environments was high and Eh low. These conditions favoured bacterial sulphate reduction and resulting H₂S reacted with Fe²⁺ and organic peat compounds to form pyrite and organic sulphur components. Inertinite precursors formed when the water table was low and Eh high; aerobic respiration prevailed and little H₂S was produced. Organic sulphur derived from peat-forming plant tissue is dominant in intertinite-rich low-sulphur coal; pyritic sulphur exceeds organic sulphur in high-sulphur coals dur to preferential reaction of H₂S with Fe²⁺.     

Composition of soluble organic matter in coals: relation to rank and liptinite fluorescence

Study of a series of twenty-six German high volatile bituminous B to low volatile bituminous coals of Upper Carboniferous age by recently refined analytical methods (‘flow-blending’ extraction, medium pressure liquid chromatography, HPLC, glass capillary gas chromatography and spectral fluorescence microscopy) reveals that yield and composition of soluble organic matter are strongly controlled by rank. In particular, the following points of inflection are noted in rank trends around 0.9% vitrinite reflectance: a maximum in yields of total soluble organic matter, aromatic hydrocarbons and n-alkanes; the most pronounced change in aromatic hydrocarbon composition; a trend reversal for pristane/ phytane ratios; a gradient change in the odd/even-predominance of long chain n-alkanes; appearance of a bimodal n-alkane distribution; and a sharp drop in concentration of individual n-, and isoprenoid alkanes. This discontinuity in rank trends around 0.9% Rm is interpreted to reflect a major change in reaction types, i.e. a shift from predominantly hydrocarbon generating to predominantly fragmentation reactions. Rank trends of maceral fluorescence exhibit the following pronounced changes over a similar but broader rank range: Different types of the maceral sporinite show a relatively abrupt shift of the fluorescence colour from yellow towards red between 0.8–0.9% Rm while up to about 1.0% Rm a sharp increase is recorded in the proportion of fluorescent vitrinite. This coincidence at a near-equal rank stage suggests a common cause for changes in yield and composition of the soluble organic matter and the maceral fluorescence of these coals.     

Relationship between the technical parameters of cokes produced from blends of three Polish coals of different coking ability

The demand for metallurgical coke for blast furnaces is forcing the coking industry to look for new sources of coking coals. The physical and chemical parameters of coals used in coking blends determine the quality (reactivity and strength) of the finished cokes. This study examines the technical properties of the cokes produced from various blends of three Polish coals with different coking. These coals were collected from three mines: Zofiówka, Szczygłowice, and Krupiński (Upper Silesian Coal Basin, Poland). The coal charges were coked in the laboratory scale, at temperatures of up to 1000 °C, in an inert atmosphere. The coke reactivity (index CRI) and the coke strength after reaction (CSR) were measured and correlated to the properties of parent coals using statistical analysis. The result of this study shows strong relationships between the concentration of the best coking coal (Zofiówka) in the blend and the CRI and CSR of the resulting coke. The CRI and CSR parameters for cokes obtained from single coals and from their blends show the additive character. This study also confirms the linear relationship between CRI and CSR parameters of the cokes.