Stratigraphy,palynology and geochemistry of the Lower Eocene coals of Arauco,Chile

The Arauco Sedimentary basin of Chile (37° −37° 45′S, 73° 08′ −73° 41′W) contains the most important reserves of bituminous coals of Chile. These are concentrated in two Formations: Curanilahue (Lower Eocene) and Trihueco (Middle Eocene). Five coal seams from the Lota Member of the Curanilahue Formation have been studied from the stratigraphic, palynologic and geochemical point of view. These coals were formed during a regressive stratigraphic episode; the palynological assemblage indicates that the climatic conditions prevailing at the time were of high humidity and temperature. These coals from a geochemical point of view are characterized by high sulphur (2.02%), ash (11.9%) and Ge (67.5 ppm; 1224.3 ppm in ash).     

Coalification levels and their significance in the groundhog coalfield,North-Central British Columbia

The only significant deposits of anthracite and meta-anthracite in Canada occur in Upper Jurassic-Lower Cretaceous strata of the Groundhog coalfield in northcentral British Columbia. The coal rank in the coalfield varies from low volatile bituminous (1.70% R_{0 max}) to meta-anthracite (5.8% R_{0 max}). The main coal bearing unit, the Currier, includes up to 17 seams of anthracite and meta-anthracite most of which are less than 1 m thick. In the McEvoy unit, which overlies the Currier, up to 9 coal seams, mainly of semi-anthracite, occur that are up to 0.8 m thick. The coals are variably argillaceous, locally sheared and cut by quartz and less commonly, by carbonate veins. Coalification gradients in the coalfield vary from 0.8% to 3.0% R_{0 max} km^?1. The rank of coal within both the McEvoy and Currier units appears to increase towards the eastern edge of the coalfield.The level of coalification and the coalification gradients in the coalfield are anomalously high considering an indicated maximum depth of burial of 3500 m. From comparison with coalification models it appears that geothermal gradients in the order of 50° to 70°C/km must have existed for a period of time measured in millions of years. Studies to date suggest the coalification is pre-tectonic and thus pre-Late Cretaceous although there is some evidence for high heat flow in the Tertiary. The origin of the high heat flow may be related to intrusion accompanying collision of the Stikine terrain with the early Mesozoic margin of North America and/or high heat flux over an easterly dipping subduction zone below the Coastal volcanic-plutonic arc to the west.     

Arsenic in coal: a review

The review presented covers: (a) historical introduction; (b) some analytical comments; (c) some peculiarities of the As geochemistry in environment; (d) an estimation of coal Clarke value of As; (e) some coals enriched in As; (f) mode of As occurrence in coal; (g) factors influencing the As distribution in coal matter and coal bed; (h) genetic topics; (i) some topics related to environmental impact of As by the coal combustion.The World average As content in coals (coal Clarke of As) for the bituminous coals and lignites are, respectively, 9.0±0.8 and 7.4±1.4 ppm. On an ash basis, these contents are higher: 50±5 and 49±8 ppm, respectively. Therefore, As is a very coalphile element: it has strong affinity to coal matter — organic and (or) inorganic but obligatory authigenic. The coalphile affinity of As is like that for Ge or S.There is strong regional variability of As distribution due to geologic variability of the individual coal basins. For example, bituminous coals in Eastern Germany, Czech Republic and SE China are enriched in As, whereas the coals in South Africa or Australia are very depleted compared to coal Clarke of As. In general, some relationship exists between As content and its mode of occurrence in coals. Typically, at high As content, sulphide sites dominate (pyrite and other more rare sulphides), whereas at low As content, As_org dominates, both being authigenic. A contribution of the terrigenic As (in silicates) is usually minor and of the biogenic As_bio (derived from coal-forming plants) is poorly known.Both organic and inorganic As can exist not only as chemically bound form but also in the sorbed (acid leacheable) arsenate form. With increasing coal rank, sorbed exchangeable arsenate content decreases, with a minimum in the coking coals (German data: the Ruhr coals).Relations of As content in coal to ash yield (or its partitioning in sink–float fractions) and to coal petrographic composition are usually complicated. In most cases, these relations are controlled by main site (form) of As — As_pyr or As_org. If As_pyr dominates, an As accumulation in heavy fractions (or in high-ash coals) is observed, and if As_org dominates, it is enriched in medium-density fractions (or low- and medium-ash coals). Arsenic is in part accumulated in the inertinite vs. vitrinite (As_org ?).There are four genetic types of As accumulation on coal: two epigenetic and two syngenetic: (1) Chinese type—hydrothermal As enrichment, sometimes similar to known Carlin type of As-bearing telethermal gold deposits; (2) Dakota type—hypergene enrichment from ground waters draining As-bearing tufa host rocks; (3) Bulgarian type—As enrichment resulting from As-bearing waters entered coal-forming peat bogs from sulphide deposit aureoles; (4) Turkish type—volcanic input of As in coal-forming peat bog as exhalations, brines and volcanic ash.During coal combustion at power plants, most of the initial As in coal volatilizes into the gaseous phase. At the widely used combustion of pulverized coal, most of As_org, As_pyr and “shielded” As-bearing micromineral phases escape into gaseous and particulate phase and only minor part of As_clay remains in bottom ash. The dominant fraction of escaping As is in fly ash. Because 97–99% of the fly ash is collected by electrostatic precipitators, the atmospheric emission of As (solid phase and gaseous) is usually assumed as rather minor (10–30% from initial As in coal). However, fly ash disposal creates some difficult environmental problems because it is potentially toxic in natural waters and soils. The As leaching rate from ash disposal is greatly controlled by the ash chemistry. In natural environment, As can be readily leached from acid (SiO₂-rich) bituminous coal ashes but can be very difficult from alkali (CaO-rich) lignite ashes.If the As_pyr form dominates, conventional coal cleaning may be an efficient tool for the removing As from coal. However, organic-bound or micromineral arsenic (“shielded” grains of As-bearing sulphides) are not removed by this procedure.Some considerations show that “toxicity threshold” of As content in coal (permissible concentration for industrial utility) may be in the range 100–300 ppm As. However, for different coals (with different proportions of As-forms), and for different combustion procedures, this “threshold” varies.     

煤中砷的赋存状态

砷是煤中常见的有害微量元素,由于其丰度较低,定量研究其赋存状态一直很困难。近年来,采用逐级化学提取实验方法对煤中不同赋存状态的砷进行了定量研究,综合分析这些研究可得出以下结论：①煤中砷的赋存状态包括硫化物态砷、有机态砷、砷酸盐态砷、硅酸盐态砷、水溶态和可交换态砷。总体上,硫化物态砷＞有机态砷＞砷酸盐态砷＞硅酸盐态砷＞水溶态和可交换态砷,但在不同的煤样品中,也表现出较大的差异性。②一般而言,煤中大部分砷存在于含砷黄铁矿中,含砷黄铁矿中的砷含量与黄铁矿的成因或类型有关。煤中的砷酸盐态砷主要与铁氧化物和氢氧化物共生;硅酸盐态砷主要进入粘土矿物晶格。③在砷含量较低的煤样品中,有机态砷含量较高,其中在褐煤和低煤级烟煤中,可提取出与腐殖酸和富里酸结合的砷。当前还难以确认有机态砷的化学结构。④贵州特高砷煤中砷的赋存状态较为复杂,在某些样品中与氧结合的有机态砷为主要的赋存状态。     

宁夏煤变质规律初探

宁夏煤炭资源丰富,煤类多,在区域和垂向上呈现出明显的规律性。晚古生代煤层以中、高变质的烟煤、无烟煤为主,中生代煤层以低变质的烟煤为主,从各含煤区分布看,贺兰山、香山含煤区多为高变质的烟煤和无烟煤,灵盐、固原含煤区以低变质烟煤为主,青铜峡-固原深断裂西部的煤变质程度明显高于东部。分析认为深成变质作用对各时代煤变质具有普遍意义,在此基础上,岩浆热力变质作用和动力变质作用也是导致局部地区煤变质增高的因素,如贺兰山含煤区的汝箕沟矿区,受隐伏岩浆热力影响,以岭大井田为中心,呈现北东向展布的半环带状煤级分带;香山含煤区各时代煤类分布方向与区域构造线方向一致,推测可能在深成变质作用下叠加了岩浆热力变质和动力变质作用。     

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.     

A petrologic method of analysis of nonmaceral microstructures in coal

The petrographic maceral composition and vitrinoid reflectance of bituminous coals have been correlated with their carbonization characteristics and are widely used to predict how coals will perform in the coking process and to calculate the strength of the resulting coke. As a result, there is a growing dependence on coal petrographic data in characterizing coals for cokemaking. In addition, there is a growing awareness that there are other nonmaceral microstructures in coal such as material size, shape, association, fracturing, and weathering which should permit better characterization of coals when properly interpreted. These nonmaceral microstructures also give an insight into the metamorphic history and changes due to burial and exhumanation.To expand the use of coal petrologic and petrographic data, a new analytical procedure has been developed that requires the microscopic determination of such nonmaceral microstructures as normal coal, coal fines, pseudovitrinoids, microbrecciation, oxidation, coarse mineral matter, miscellaneous materials, and contamination. The occurrence of one or more of these microstructures in coal, depending on their kind and abundance, may have a significant effect on the coal performance in various processes. This work has resulted in formulation of a technique for determining the nonmaceral microstructures in coal and, if applied as a supplement to the routine maceral analysis of coals, should help in explaining the anomalous behavior of some coals.     

Solid state 13C-NMR spectroscopy of some oligocene coals of Assam and Nagaland

Five representative sub-bituminous coals from NE part of India have been analyzed with respect to their distribution of carbon functional groups through ¹³C solid state NMR experiments. The ¹³C Cross Polarised/Magic Angle Spinning NMR spectra of the coal samples were recorded at temperatures of 23°C, 50°C and 70°C respectively and the changes on their structures were interpreted. The NMR spectra of low rank coals were found to exhibit varying degrees of fine structures. The aromaticities of the coal were also determined from the C/H ratios of coal. Some changes in the peak positions along with the formation of simple aromatic units were observed on mild heating.     

Clays and other minerals in coal seams of the Moura-Baralaba area, Bowen Basin, Australia

The clays and other minerals in a succession of Late Permian coals of high-volatile bituminous to semi-anthracite rank have been identified, using low-temperature oxygen plasma ashing and X-ray diffraction, and evaluated to identify the relative roles in mineral matter formation of detrital input, early diagenesis in the peat swamp and late diagenesis associated with rank advance. Although well-ordered kaolinite of probable early diagenetic origin is abundant throughout the succession, the uppermost and lowermost seams of the sequence, regardless of rank, contain relatively abundant illite and/or interstratified illite/smectite, along with a small but significant proportion of chlorite. These clays are thought to be essentially of detrital origin, washed or blown into the peat deposit in relative abundance during the establishment and subsequent overwhelming of an extensive and long-lived swampy environment. Quartz is also abundant in the lower seams of the sequence, especially close to the regional sediment source area. Illite is unusually abundant in the topmost seam in both high- and low-rank parts of the succession, and thus appears to represent detrital input from a particular source material. Although significant changes are reported in the clays of the associated strata due to rank advance, the principal effect of rank advance on the minerals in the coal itself appears to be the development of an ammonium illite, and possibly some additional fine-grained chlorite, in the semi-anthracite material. Isolation within the organic matter of the coal is thought to have inhibited access for ions such as K⁺, which might otherwise have become involved in metamorphic reactions and given rise to mineralogical changes commonly found in non-coal sedimentary successions.     

On the effects of petrographic composition on coalbed methane sorption

The effect of petrographic composition on the methane sorption capacity has been determined for a suite of coals and organic-rich shales. Subbituminous and bituminous coals were separated into bright and dull lithotypes by hand-picking. The methane sorption capacities range between 0.5 and 23.9 cm³/g at a pressure of 6 MPa. The low volatile bituminous Canmore coal and the anthracite sample have the highest capacities with the “natural coke” having the lowest. For low-rank coals there is no significant difference between bright and dull samples except for one coal with the dull sample having a greater sorption capacity than its bright equivalent. For higher-rank coals, the bright samples have a greater methane capacity than the dull samples and the difference between sample pairs increases with rank. The boghead coal samples have the highest sorption capacities in the liptinite-rich coals suite and are higher than subbituminous to medium volatile bituminous samples. Pore size distribution indicates that methane is held as solution gas in liptinite-rich coals and by physical sorption in micropores in liptinite-poor coals. These contrasting processes illustrate that liptinite-rich samples need to be independently assessed. The positive relationship between reactive inertinite content and methane sorption capacity occurs within the subbituminous to medium volatile bituminous coals because the reactive inertinite is structurally similar to vitrinite and have a higher microporosity than non-reactive inertinite. Reactivity of inertinite should be assessed in CBM studies of dull coals to provide a better understanding of petrographic composition effects on methane capacity.     

Coals of Canada: Distribution and compositional characteristics

Canada's coal resources occur in 16 sedimentary basins or groups of basins and range in age from Devonian to Tertiary. The Western Canada Sedimentary Basin (WCSB), which contains the vast majority (about 90%) of the nation's coal resources of immediate interest, underlies a large area in the provinces of British Columbia, Alberta, Saskatchewan and Manitoba, extending northward to about the 62nd Parallel in Yukon and Northwest Territories. Coal deposits in the WCSB range in age from Early Carboniferous (Mississippian) to Paleocene. Rank ranges from lignite to semianthracite. About 36% of the total estimated 71,000 megatonnes of resources of immediate interest in the WCSB is bituminous coal, including a high proportion in the medium to low volatile range. Their low sulphur contents and acceptable ash levels make these medium and low volatile bituminous coals attractive 3s coking feedstocks and large quantities are mined for that purpose. The lower rank western Canadian coals are used mainly for electricity generation.Significant resources of bituminous coal occur in the coalfields of Atlantic Canada where they have been mined since 1720. Most of these coals are classed as high volatile A bituminous and most are used for power generation. Large resources of coal (lignite to anthracite) also occur in more remote regions of Canada, such as the Bowser Basin in northwestern British Columbia, and Sverdrup Basin/ Franklinian Geosyncline in the Arctic Islands. Information on distribution and compositional attributes of these frontier region coals is commonly scarce.     

Petrologic studies of terrestrial organic matter in Carpathian flysch sediments, southern Poland

In the Carpathian Flysch, coal is present either as exotics of Carboniferous coal deposits or as autochthonous, thin layers of lustrous coal. This paper present the results of the studies of coal-bearing rocks that are coeval with the enclosing flysch sediments. These coals form lenses up to 0.15 m thick. Their morphology precludes an exotic origin. The main petrographic component is collinite with admixtures of poorly fluorescing telinite. Minor components are: exudatinite, sporinite, fusinite, micrinite and sclerotinite. Mineral matter consists of framboidal pyrite clay minerals and quartz.The random reflectance of telocollinite varies from 0.38% to 0.72%, which corresponds to subbituminous and bituminous ranks. Correlation between chemical analysis, coking properties and relfectance measurements, leads to the conclusion that boundary between subbituminous and bituminous coals should be defined by the following values: C=80wt%, VOLATILES=43wt%; calorific VALUE=32.3 MJ/kg; and R^o=0.56–0.57%.Atypical properties, such as: upper C value (75–80wt%); high volatile matter contents (over 43wt%) and low random reflectance (^o about 0.38–0.57%) in subbituminous coals; low C value (about 80–82wt%); low reflectance (0.56–0.72%); and good coking properties, of the bituminous coals are attributed to quick coalification during increasing temperature as a result of tectonic stress.     

Possibilities of the utilization of micropetrographic parameters in the scientific classification of bituminous coals

Proposals for new scientific classifications of bituminous coals are based on micropetrographic parameters, i.e. vitrinite reflectance as a criterion of the coalification and maceral composition, presupposed to express the connection between the genetic peculiarities and physical, chemical, and technological properties of the coal mass. In the case of coals with high inertinite contents, however, the utilizability of these parameters meets with difficulties resulting from the subjectivity of determining the different transitional material and from insufficient knowledge of inertinite behaviour at higher temperatures. In the case of the maceral-variable bituminous coals produced in the Ostrava-Karviná Coal Basin, these insufficiencies are not important since it is especially the expression of the variability of the properties of isometamorphic vitrinites, which has decisive effects up-on the course of the thermo-chemical transformations, that is of principal importance to the scientific classification of these coals.In the first approximation, the properties of isometamorphic vitrinites may be expressed by the parameter (H/O)_at, closely connected with fluidity. While the micropetrographic parameters reflect in particular the peculiarities in the chemical structure of the aromatic parts of coal macromolecules, the parameter (H/O)_at expresses the properties of the non-aromatic structures of vitrinite, significantly affecting the course of its thermal degradation. The experimental results show that the value of the parameter (H/O)_at, fluidity and the course of degassing the coal of a lower coalification are independent of the maceral composition and vitrinite reflectance; also that the caking and coking properties of low-rank coals are especially dependent on the parameter (H/O)_at and partially on the micropetrographic parameters. All these facts should be taken into consideration in preparing new scientific classifications of bituminous coals.     

An evaluation of Rock-Eval pyrolysis for the study of Australian coals including their kerogen and humic acid fractions

Rock-Eval pyrolysis was performed on lithotype and depth profiles of Tertiary brown coals and a coalification profile of Permian bituminous coals. The humic acid and kerogen fractions from the coals are also investigated by this technique along with the effect of base extraction on the kerogen fraction. Structural variations between brown coal lithotypes are primarily reflected by changes in Oxygen Index Value. This result was supported by the results from the depth profile (same lithotype). A wide range of Hydrogen Indices (independent of depth) but similar Oxygen Indices were observed. The results from the Qualification profile show that the Oxygen Indices varied with rank, whereas Hydrogen Indices show a greater dependence on coal type. A plot of $\text{H}\text{C}$versus Hydrogen Index produced good correlations with the brown (0.77) and bituminous (0.90) samples lying on two separate lines intersecting at high H/C. This result (and higher correlation for bituminous samples) reflects the expected dependence of hydrogen index on oxygen content (present primarily as hydroxyl groups). A high correlation (0.95) between quantitative IR data (K 2920 cm mg^?1) and Hydrogen Indices supports previous conclusions regarding the dependence of Hydrogen Indices on the aliphatic structure of the samples.     

Initial volatilization temperatures and average volatilization rates of coal — Their relationship to coal rank and other characteristics

Two thermal parameters, initial volatilization temperature (IVT) and average volatilization rate (AVR), have been determined by thermogravimetric analysis in argon for 38 coal samples ranging in rank from lignite to low-volatile bituminous. Both IVT and AVR are correlated with percent volatile matter and vitrinite reflectance.The IVT values increase gradually from about 250 to 445°C with increasing rank; however, a change in slope is observed in the region of high-volatile bituminous coals (from about 340°C to about 380°C) when IVT's are plotted against percent volatile matter or percent fixed carbon. The changes in slope near 340°C and near 380°C occur at “coalification jumps” recognized on the basis of changes in the optical and chemical character of the macerals. In general, AVR values decrease gradually with increasing rank for the lignite and sub-bituminous coals and for the medium- and low-volatile bituminous coals; however, a sharp increase in AVR occurs in high-volatile bituminous coals. The change in slope of the IVT curves and sharp increase in the AVR values for high-volatile bituminous coals reflect the development of new, higher vapor pressure organic compounds produced during this stage of the coalification process.A plot of AVR vs IVT reveals three regions which correspond to: (1) lignite and sub-bituminous coals; (2) high-volatile bituminous coals; and (3) medium- to low-volatile bituminous coals.     

Oil-generating potential of Tertiary coals and other organic-rich sediments of the Nyalau Formation,onshore Sarawak

The oil-generating potential of coals and other organic-rich sediments from the Late Oligocene–Early Miocene Nyalau Formation, the offshore extension of which is believed to be a major source rock, is evaluated. Coals of the Nyalau Formation are typically dominated by vitrinite, with moderate and low amounts of exinite and inertinite, respectively. Significant amounts of clay minerals are present in these coals and those containing between 15 to 65% mineral matter by volume are termed carbargilite. The samples analysed range from sub-bituminous to high-volatile bituminous rank, possessing vitrinite reflectance in the range 0.42% to 0.72%. T_max values range from 425°–450°C which is in good agreement with vitrinite reflectance data. Good oil-generating potential is anticipated from these coals and carbargilites with moderate to rich exinite content (15–35%). This is supported by their high hydrogen indices of up to 400 mgHC/gTOC, Py–GC (S2) pyrograms with n-alkane/alkene doublets extending beyond nC₃₀, and their being in the early to mid-mature oil-window range. Petrographically, the most significant evidence of the oil-generating potential of these coals is the generation of petroleum-like materials (exsudatinite) visible under the microscope. Exsudatinite is a secondary maceral, commonly considered to represent the very beginning of oil generation in coal, which is shown here to also have an important role to play in hydrocarbon expulsion. The precursor of exsudatinite in these coals is the maceral bituminite which readily expels or mobilizes to hydrocarbon-like material in the form of oil smears and/or exsudatinite as observed under the microscope. The maceral bituminite is considered to play a major generative role via early exsudatinite generation, which is considered to facilitate the overall expulsion process in coaly source rocks.     

Structural investigations of Australian coals—III. A 13C-NMR study on the effects of variation in rank on coal humic acids

A quantitative ¹³C-NMR technique was applied to humic acids, isolated from total solvent extracts obtained from coals, varying in rank from lignite to medium volatile bituminous. The results from elemental analysis and ¹³C-NMR structural ratios are interpreted in the form of three distinct structural phases in the maturation of coal humic acids. These phases reflect the rank of the parent coals. A decrease in polar functional group content and corresponding increase in aromaticity is observed with increasing maturation of humic acid chemical structure. Limits are postulated for the oxygen content and level of aromaticity for humic acids derived from higher rank coals.     

Geological and geochemical characteristics of high arsenic coals from endemic arsenosis areas in southwestern Guizhou Province,China

Southwest Guizhou Province is one of the most important areas of disseminated, sediment-hosted-type Au deposits in China and is an important area of coal production. The chemistry of most of the coals in SW Guizhou is similar to those in other parts of China. Their As content is near the Chinese coal average, but some local, small coal mines contain high As coals. The highest As content is up to 3.5 wt.% in the coal. The use of high As coals has caused in excess of 3000 cases of As poisoning in several villages. The high As coals are in the Longtan formation, which is an alternating marine facies and terrestrial facies. The coals are distributed on both sides of faults that parallel the regional anticlinal axis. The As content of coal is higher closer to the fault plane. The As content of coal changes greatly in different coal beds and different locations of the same bed. Geological structures such as anticlines, faults and sedimentary strata control the distribution of high As coals. Small Au deposits as well as Sb, Hg, and Th mineralization, are found near the high As coals. Although some As-bearing minerals such as pyrite, arsenopyrite, realgar (?), As-bearing sulfate, As-bearing clays, and phosphate are found in the high As coals, their contents cannot account for the abundance of As in some coals. Analysis of the coal indicates that As mainly exists in the form of As⁵⁺ and As³⁺, perhaps, combined with organic compounds. The occurrence of such exceptionally high As contents in coal and the fact that the As is dominantly organically associated are unique observations.     

液氮溶浸对不同煤阶含水煤样渗流特性的影响

中国包含多种煤阶煤层,由于煤质、地质条件等差异,不同煤层中的水分赋存情况也具有较大差异性。煤阶、饱水度作为影响液氮低温致裂效果的两个重要因素,有必要对其进行深入研究。为此,分别选择褐煤、烟煤与无烟煤3种煤阶煤样,并制备得出饱水度分别为0%、33%与99%的煤样进行液氮溶浸处理,使用摄像机定点拍摄、观察煤样表面宏观裂隙处理前后的演化规律,并对煤样进行氮气渗流试验。试验结果表明：液氮溶浸后褐煤因产生的一条与多条贯穿裂隙发生整体结构上的断裂,烟煤表面有新裂隙产生,原生宏观裂隙有一定的扩展与延伸,无烟煤表面宏观裂隙无明显发育;煤样饱水度越高,液氮的致裂增透效果越显著;液氮溶浸对3种煤阶煤样的致裂增透效果关系为：褐煤>烟煤>无烟煤,在完全干燥状态下,由于热应力不足以破坏颗粒间链接,烟煤与无烟煤的增透效果近似相等;对于褐煤,液氮溶浸处理对完全干燥状态下的煤体即产生有效致裂,渗透率平均增幅高达559.35%,对于烟煤,在饱水度为33%和99%的状态下,液氮溶浸对煤体具有明显致裂效果,渗透率平均增幅分别为330.60%和448.77%,对于无烟煤,在饱水度为99%的状态下液氮溶浸处理才能对煤体产生有效致裂,渗透率平均增幅为185.53%。     

Developments in high-resolution solid-state13C NMR spectroscopy of coals

The recent development of “second generation” NMR experiments on coals is discussed in this paper. Such experiments have three aims: (1) To determine the extent to which quantitative aromaticity measurements can be made on coals by cross polarization-magic angle spinning (CP/MAS); (2) To obtain more detailed information on coal structure and reactivity than that given by the simple aromaticity measurements possible at the time; (3) To follow reaction pathways when coal is chemically modified. In this plenary lecture the relevant literature is reviewed, and new experimental work in all three areas outlined above is reported. Experimental evidence is presented which shows that aromaticity measurements on a bituminous coal by cross polarization (CP) or single pulse techniques give identical results. Relaxation data for naphthalene polymers suggest that these structures in coal are seen in CP experiments. Dipolar dephasing experiments suggest that the average size of the coal vitrinite molecule does not increase with increase in coal rank due to aromatic substitution reactions. Various relaxation experiments demonstrate how different carbon types can be distinguished in both¹³C-labelled and unlabelled coals.