Chemistry of alkali extraction of brown coals—I. Kinetics, characterisation and implications to coalification

Three Australian brown coals have been separated into humin and humic acid fractions and studied by high resolution solid state ¹³C NMR spectroscopy and Fourier transform IR spectroscopy. The aromatic rings of the humic acids are highly substituted showing that extensive cross linking must have occurred during formation from wood lignin and tannin. However, the humins contain more aliphatic carbon and hydrogen than the corresponding humic acids. This shows that little cross linking has occurred with other components of the brown coal such as resins, waxes cutin and algal detritus, and cross linking has not rendered the aromatics alkali insoluble. The kinetics of extraction are complex and not simple first order. This is reflected in the chemical composition of the humic acid which is extraction temperature dependent. We also observed that there is a conversion of aromatic carbon to aliphatic carbon and gas during extraction, probably by alkaline oxidation, resulting in ring opening. A range of suitable model compounds have been studied to confirm this finding. Such a mechanism may account for the modification of lignin in oxidising environments such as those occurring in the initial stages of coalification (lignite or brown coal formation) and in soils.     

高磁场固态碳13核磁共振法研究干酪根的热降解成烃机理

用高磁场(75.46MH_Z)固态碳13核磁共振(NMR)波谱仪研究了抚顺油页岩在热降解模拟试验中干酪根的化学结构变化.为了消除旋转边带的干扰,在应用交叉极化与魔角自旋(CP/MAS)技术的同时,采用了Dixon TOSS技术,从而得到高分辨的波谱图。据此测定了热降解过程中干酪根各种碳结构组成的变化,计算了芳碳率、亚甲基基团平均碳原子数、环缩合指数等一系列干酪根的结构参数,并与干酪根的相对产油潜力相关联.发现干酪根的产油潜力直接与亚甲基基团的含量有关,而芳碳以及与芳碳相连的甲基碳则贡献甚微.文中还对干酪根的热降解成烃机理作了探讨。     

次火山热变质煤的物理测试特征

样品采自伊敏褐煤盆地中一个因次火山活动形成的烟煤区,包含了从褐煤到瘦煤的变质系列。红外光谱分析表明,煤的含氧基团在褐煤阶段已开始消失,烷基和芳环同步增加,在R°=1.10%时达最大值。顺磁共振自由基浓度和X-衍射参数La/Lc介于区域变质煤和岩浆接触热变质煤之间,芳核外官能团的热演化超前于芳核骨架及R°的演化。      

Comparison of physical and chemical properties of maceral groups separated by density dradient centrifugation

Eight coals have been selected for study of the physical and chemical properties of the maceral group . The density-gradient centrifugation technique was employed to affect maceral group separation. The maximum reflectance method of Ting and Lo was used for estimating the reflectance of very small coal particles. The reflectograms were used to characterize the separated maceral fractions. The density, elemental composition, reflectance, NMR parameters of aromaticity, protonated aromatic carbon content and ƒ_stuggereda^stuggeredH of the maceral groups were compared. Variations in the aromatic structure of the maceral groups are discussed as well as the observation that ƒ_stuggereda and ƒ_stuggereda^stuggeredH change with particle density.     

扎鲁特地区无烟煤分子结构特征和模型构建

为了构建内蒙古扎鲁特地区无烟煤的分子结构模型,采用工业分析、元素分析、核磁共振碳谱、高分辨率透射电镜和X射线光电子能谱等测试方法对该地区无烟煤的分子结构进行研究。结果表明无烟煤分子结构中以芳香碳为主,脂肪碳以短烷基侧链和环烷烃为主。煤分子结构中氧原子主要以酚羟基和醚氧基的形式存在,氮原子主要以吡咯型氮和吡啶型氮的形式存在,硫原子主要的赋存形态是硫醇硫酚。结合由核磁共振碳谱测得的煤结构参数和由高分辨率透射电镜测得的芳香环尺寸和含量,构建了无烟煤大分子平均结构模型。对构建的模型进行了结构优化与能量分析,发现煤分子结构的芳香片层趋于平行排列,非键结势能中的范德华力是保持煤结构稳定的主要因素。本研究为采用分子动力学模拟从分子尺度研究扎鲁特地区无烟煤在石墨化过程中,其芳香碳层的拼叠过程及其反应路径提供了模型基础。      

Cyclic terpenoids of contemporary resinous plant detritus and of fossil woods, ambers and coals

Cyclic terpenoids present in the solvent extractable material of fossil woods, ambers and brown coals have been analyzed. The sample series chosen consisted of wood remains preserved in Holocene to Jurassic sediments and a set of of ambers from the Philippines (copalite), Israel, Canada and Dominican Republic. The brown coals selected were from the Fortuna Garsdorf Mine and Miocene formations on Fiji.The fossil wood extracts contained dominant diterpenoid or sesquiterpenoid skeletons, and aromatized species were present at high concentrations, with a major amount of two-ring aromatic compounds. Tricyclic diterpenoids were the predominant compounds in the ambers. Aromatized derivatives were the major components, consisting of one or two aromatic ring species with the abietane and occasionally pimarane skeletons. The saturated structures were comprised primarily of the abietane and pimarane skeletons having from three to five carbon (C₁, C₂, etc.) substituents. Kaurane and phyllocladane isomers were present in only minor amounts. Bicyclic sesquiterpenoids as saturated and partial or fully aromatized forms were also common in these samples, but only traces of sesterterpenoids and triterpenoid derivatives were found.The brown coal extracts were composed of major amounts of one- and two-ring aromatized terpenoids, with a greater proportion of triterpenoid derivatives than in the case of the woods and ambers. This was especially noticeable for the German coal, where the triterpenoids were predominant. Open C-ring aromatized structures were also present in this coal. Steroid compounds were not detectable, but some hopanes were found as minor components in the German brown coal.An overview of the skeletal structure classes identified in each sample, as well as the general mass spectrometric characteristics of the unknown compounds are included in the present paper. It can be concluded from these structural distributions that aromatization is the main process for the transformation of terrestrial cyclic terpenoids during diagenesis, constituting a general pathway for all terpenoids.     

Doppleritization of xylitic coal in the light of petrographic and chemical investigations

The paper presents the results of petrographic and chemical investigations of xylitic coal, xylite and their ash. As is known, a xylitic coal has the function of a lithotype whereas xylites are inclusions brown coals only. All these xylites were arranged according to the increasing degree of doppleritization of xylem in the sequence: common xylite, poorly, moderately and intensely doppleritized varieties, dopplerite coal. The distinctive criteria were their differentiated physical properties, which are also reflected in the variable petrographic and chemical compositions. The petrographic differences result from the replacement of textinite by ulminite and gelinite, while the differentiation of the chemical constitution is due to the increasing carbon content and the increasing number of functional groups that determine the aromatic nature of the internal structure of the coal. Infrared absorption spectroscopy, Raman spectroscopy and chemical analysis of ash have shown that the aromatization of coal and the resulting increase in the degree of order of the structural unit are due to the formation of organomineral compounds in the course of doppleritization. It appears from the investigations that the doppleritization of vegetable matter gives rise to gels that are a mixture of organo-mineral humic compounds. The process of humification leads to the formation of gel made up of humins. It follows then that there are two ways of initial coalification of plant material, both referred to as biochemical gelification.     

Nuclear magnetic resonance spectroscopy of soils and related materials. Relaxation of 13C nuclei in cross polarization nuclear magnetic resonance experiments

Relaxation of ¹³C nuclei in a peat, a soil, and three soil fractions have been investigated in order to improve structural resolution and to investigate quantification of various carbon types. Rotating frame spin lattice relaxation times (T_1?'s) and transverse relaxation times (T₂′'s) are similar to those observed for coals. T₂′'s of carbons in different magnetic environments differ sufficiently that spectra can be obtained containing only nonprotonated carbon and methyl substituents if a 40 μsec delay without decoupling is inserted into the pulse programme before data acquisition (dipolar dephasing). Provided quantitative data is obtained in simple cross polarization experiments and allowance is made for loss in signal intensity of nonprotonated carbon during dipolar dephasing, then the fraction of aromatic carbon which is protonated in the samples can be determined.     

低熟煤型气的成因化学

用水介质热压模拟、_１３Ｃｎｍｒ分析表明，Ｒｏ＝０.７%以前，煤型有机质中的芳环结构的变化主要是官能团的变化，芳环仍然保留着单环的结构特征，并未发生明显的缩合作用。即在早期热演化过程中由邻甲氧基苯酚结构向邻苯二酚类结构转化，进而转化为烷基酚类结构，同时脱去甲氧基中的甲基。甲氧基含量从Ｒｏ＜０.３%开始迅速减少，到Ｒｏ＝０.７%时已基本脱除完毕。煤型有机质中的甲氧基在热演化早期通过自由基反应脱去甲基，对低熟煤型气有重要贡献。     

Chemical changes during natural oxidation of a high volatile bituminous coal

Core drilling of near surface seams near Wakefield NSW has provided high volatile bituminous coal samples that have been subject to varying degrees of natural in situ oxidation. Five levels of oxidation have been defined, mainly on visual evidence, ranging from unoxidised coal to highly oxidised material. Samples of each oxidation level have been investigated by chemical analysis, Fourier transform infrared spectroscopy (FTIR) and solid state carbon-13 nuclear magnetic resonance spectroscopy (NMR) with cross-polarization and magic angle spinning.The results show that mineral matter, moisture and oxygen content increase with oxidation, whereas carbon, hydrogen and specific energy decrease. Moisture determination is suggested as a quick, facile method for indicating the oxidation level for a coal sample from this seam. FTIR showed a marked loss of aliphatic C-H groups with increasing oxidation, and an increase in carbonyl and carboxylate groups. Aromatic C-H groups were much less affected by oxidation. Solid state carbon-13 NMR showed increasing carbon aromaticity with oxidation, but showed substantial carbonyl carbon only at the highest oxidation level. No evidence was found for an increase in aromatic substituents during oxidation; if anything, there is a small decrease in substituents.     

Occurrence and geochemical significance of 1,2,5,6-tetramethylnaphthalene

Analysis of aromatic hydrocarbon fractions of selected coal and shale samples reveals the predominance of two specific polyalkylnaphthalenes which have been identified as 1,2,5-trimethylnaphthalene and 1,2,5,6-tetramethylnaphthalene. The maturity of the samples is such that the source effect on the formation of individual molecules from biological precursors is expected to be recognisable. These alkylnaphthalenes are thought to be diagenetically derived from pentacyclic triterpenoids via 8,14-seco-triterpenoids, which are also detectable in some of the samples investigated. It is proposed that 1,2,5,6-tetramethylnaphthalene, in the coal samples, is formed by cleavage and methyl shift reactions from geminal C-4-methylated triterpenoids which contain a leaving group in position 3. For the shale samples, degradation of monoaromatic secohopanoids must be considered as an alternative pathway.     

Reconstruction of floral changes during deposition of the Miocene Embalut coal from Kutai Basin,Mahakam Delta,East Kalimantan,Indonesia by use of aromatic hydrocarbon composition and stable carbon isotope ratios of organic matter

The distribution of aromatic hydrocarbons and stable carbon isotope ratios of organic matter in a series of nine Miocene Embalut coal samples obtained from nine coal seams of Kutai Basin, East Kalimantan, Indonesia were studied. The rank of the Embalut coals ranged from lignites to low rank sub-bituminous coals (0.36–0.50% Rr), based on measurements of huminite reflectance. The aromatic hydrocarbon fractions of all coal samples were dominated by cadalene in the lower boiling point range and picene derivatives in the higher boiling point range of the gas chromatograms. Cadalene can be attributed to the contribution of Dipterocarpaceae and various hydrated picenes to the contribution of additional angiosperms to the coal forming vegetation. The picenes originate from alpha- and beta-amyrin. However, in some coal samples minor amounts of simonellite and retene were also detected which argues for an additional contribution of gymnosperms (conifers) to coal forming vegetation preferentially in the Middle Miocene and at the beginning of the Late Miocene. The results of stable carbon isotope ratios (δ¹³C) in most of the coal samples are consistent with their origin from angiosperms (δ¹³C between ?27.0‰ and ?28.0‰). During the Miocene the climate of Mahakam Delta was not uniformly moist and cooler than the present day climate. This would have been favourable for the growth of conifers, especially in the montane forests. The contribution of conifers to the Embalut coals might be a result of the cool Middle/Late Miocene climate during peat accumulation in the Kutai Basin.     

超临界CO2对烟煤和无烟煤化学结构的影响

超临界CO₂对煤化学结构的改造对煤层CO₂封存能力极为关键。论文开展了模拟埋深1500m （62.5℃、15 MPa）条件下4组不同变质程度煤的ScCO₂-H₂O体系与煤岩地球化学反应实验。通过傅里叶变换红外光谱和X射线粉末衍射实验获得了反应前后煤化学结构演化特征,探讨了煤化学结构演化的机理。结果表明:ScCO₂作用后,煤中脂肪烃链长度普遍增加,仅肥煤的芳香烃丰度增大,肥煤、瘦煤和贫煤含氧基团丰度的增大主要由氢键基团含量的增加贡献,无烟煤含氧基团丰度则主要受低分子化合物溶出的影响。ScCO₂引起的溶胀作用造成肥煤和瘦煤芳香层面之间交联键断裂,芳香微晶内部结构疏松,而芳香层面内C_Ar-C_Ar交联的形成提高了肥煤和瘦煤芳香性和芳香环缩合度;贫煤和无烟煤中非稠合多苯结构脱落使芳香微晶内部更紧凑,脂肪烃链长度的增加则降低了贫煤和无烟煤芳香性和芳香环缩合度。      

成烃理论的发展——（Ⅱ）煤成油及其初次运移模式

近几年来，我国针对侏罗系煤系地层的油气勘探，取得了重大突破。在我国西北区的一些含煤盆地中都发现了丰富油气矿藏。煤成油的勘探开发和研究，是对陆相生油理论的重大发展，本文介绍了秦匡宗提出的一种利用＾１３Ｃ ＮＭＲ谱确定油潜力碳、气潜力碳和芳构碳评价生油气潜力的新方法，以及一种煤成烃的阶段性初次运移模式。     

Occurrences and distributions of branched alkylbenzenes in the Dongsheng sedimentary uranium ore deposits,China

A series of branched alkylbenzene ranging from C₁₅ to C₁₉ with several isomers (2–5) at each carbon number were identified in sediments from the Dongsheng sedimentary uranium ore deposits, Ordos Basin, China. The distribution patterns of the branched alkylbenzenes show significant differences in the sample extracts. The branched alkylbenzenes from organic-rich argillites and coals range from C₁₅ to C₁₉ homologues, in which the C₁₇ or C₁₈ dominated. On the other hand, the C₁₉ branched alkylbenzenes dominated in the sandstone/siltstone extracts. The obvious differences of the branched alkylbenzene distributions between the uranium-host sandstones/siltstones and the interbedded barren organic-rich mudstones/coals probably indicate their potential use as biological markers associated with particular depositional environments and/or maturity diagenetic processes. Possible origins for these branched alkylbenzenes include interaction of simple aromatic compounds with, or cyclization and aromatization reactions of, these linear lipid precursors such as fatty acids, methyl alkanoates, wax esters or alkanes/alkenes that occur naturally in carbonaceous sediments. The possible simple aromatic compounds may include substituted benzenes, functionalized compounds such as phenols that are bound to kerogen at the benzyl position, and phenols that are decomposition products derived from aquatic and terrestrial sources. The distributions of methyl alkanoates and n-alkanes were found to be different between organic-rich mudstone/coal and sandstone/siltstone. From this result, it can be concluded that such differences of the alkylbenzene distributions were mainly resulting from the differences of organic precursors, although maturity effect and radiolytic alteration cannot be completely excluded.     

Geochemical characteristics of the macromolecular part of crude and biodesulphurised flame coal density fractions

Flame coal (Janina Mine, Poland) was an object of geochemical analyses for changes caused by the process of microbial desulphurisation. Ash content, beryllium, chromium, zinc, cobalt, lithium, manganese, copper, molybdenum, nickel, lead and vanadium concentrations were investigated in coal extracts, its macromolecular part, semi-coke and polar compound fractions of extracts and pyrolysates of crude and biodesulphurised coal density fractions. The macromolecular part of extracted density fractions was pyrolysed giving semi-coke and pyrolysate. These were separated into aliphatic hydrocarbons, aromatic and polar compounds by thin layer chromatography (TLC). Distributions of aliphatic and aromatic hydrocarbons in pyrolysates of the crude and desulphurised coal density fractions were compared by gas chromatography-mass spectrometry (GC-MS). Extracts, extracted density fractions, semi-coke and polar compound fractions were analysed for concentrations of trace elements. In the crude coal their concentrations in the macromolecular part are related only to coke. However, in the desulphurised coal the participation of the particular trace element increases in pyrolysate polar compound fractions. Its values are in the range from 1% (Mn) to 100% (Cr and Mo). These changes are the best seen in the 1.80-2.30×10³ kg/m³ density fraction. Very high concentrations of trace elements were found in pyrolysate of desulphurised coal density fraction. This can be explained by the partial decomposition of coal macromolecule resulting from desulphurisation. Significant side-cleavage of peripheral groups and lighter aromatic hydrocarbons is possible. The effects of bacterial influence were manifested by the increase of polar compounds contents both in pyrolysates and extracts of the desulphurised coal and changes in distribution of aliphatic and aromatic hydrocarbon as pyrolytical products. These effects increase with mineral substance contents. Moreover, the increase of trace element concentration in coal organic matter occurs. It is reflected by the increase of participation of coal pyrolysate polar fraction in the total concentration of analysed elements in the macromolecular part of a given density fraction. The presented results are a part of the larger research aimed to find an influence of desulphurisation on chemical and technological properties of coal.     

Molecular Structure of Kerogen in the Longmaxi Shale: Insights from Solid State NMR,FT‐IR,XRD and HRTEM

Kerogen plays an important role in shale gas adsorption, desorption and diffusion. Therefore, it is necessary to characterize the molecular structure of kerogen. In this study, four kerogen samples were isolated from the organic-rich shale of the Longmaxi Formation. Raman spectroscopy was used to determine the maturity of these kerogen samples. High-resolution transmission electron microscopy (HRTEM), 13C nuclear magnetic resonance (13C NMR) , X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy were conducted to characterize the molecular structure of the shale samples. The results demonstrate that VReqv of these kerogen samples vary from 2.3% to 2.8%, suggesting that all the kerogen samples are in the dry gas window. The macromolecular carbon skeleton of the Longmaxi Formation kerogen is mainly aromatic (fa’=0.56). In addition, the aromatic structural units are mainly composed of naphthalene (23%), anthracene (23%) and phenanthrene (29%). However, the aliphatic structure of the kerogen macromolecules is relatively low (fal*+falH=0.08), which is presumed to be distributed in the form of methyl and short aliphatic chains at the edge of the aromatic units. The oxygen-containing functional groups in the macromolecules are mainly present in the form of carbonyl groups (fac=0.23) and hydroxyl groups or ether groups (falO=0.13). The crystallite structural parameters of kerogen, including the stacking height (Lc=22.84 ?), average lateral size (La=29.29 ?) and interlayer spacing (d002=3.43 ?), are close to the aromatic structural parameters of anthracite or overmature kerogen. High-resolution transmission electron microscopy reveals that the aromatic structure is well oriented, and more than 65% of the diffractive aromatic layers are concentrated in the main direction. Due to the continuous deep burial, the longer aliphatic chains and oxygen-containing functional groups in the kerogen are substantially depleted. However, the ductility and stacking degree of the aromatic structure increases during thermal evolution. This study provides quantitative information on the molecular structure of kerogen samples based on multiple research methods, which may contribute to an improved understanding of the organic pores in black shale.     

Solvent–water extraction method for the evaluation of polycyclic aromatic hydrocarbons bioavailability in coal–tar-contaminated soils

A solvent–water extraction method was proposed as an assessment tool to estimate the bioavailability of polycyclic aromatic hydrocarbons in coal–tar-contaminated soils. The approach taken was to measure the percent of polycyclic aromatic hydrocarbons extracted by a solvent–water mixture and comparing the results with the percent of polycyclic aromatic hydrocarbons degraded in a soil slurry reactor. Five soil samples from three former manufactured gas plant sites and a coal–tar disposal site which were operated between 1880 and 1947, and 1945 and 1950, respectively, in Iowa, USA were used in this study. Extraction experiments were conducted using acetone–water or ethanol–water mixtures with solvent volume fractions ranging from 1.0 to 0.4 (v/v). The percent of polycyclic aromatic hydrocarbons extracted from the various soils decreased as the volume fraction of the solvent in the solvent–water mixture was reduced. An acetone–water mixture of 0.6 was found to be appropriate in correlating the percent of polycyclic aromatic hydrocarbons degraded to the percent of polycyclic aromatic hydrocarbons extracted. For the first correlation, the percent extracted and the percent biodegraded were modified by using the molecular weights and log K _ow of polycyclic aromatic hydrocarbons, respectively. For the second correlation, the equation relating the percent extracted and the percent biodegraded was modified using soil properties such as organic carbon content and percent of clay and silt. Although the experiments were conducted for a limited number of soils, the extraction method appeared to be a good starting point in estimating the bioavailability of polycyclic aromatic hydrocarbons in coal–tar-contaminated soils.     

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.     

Carbon catalysed hydrogen exchange in petroleum source rocks

Exchange of carbon bound hydrogen has been observed when alkenes, saturated and aromatic hydrocarbons are heated at moderate temperatures on carbonaceous surfaces (activated carbon and coal). Isomerisation of alkenes and the formation of hydrogenated/dehydrogenated products from the saturated and aromatic reactants resulted. A suite of crude oils from the Carnarvon Basin (Western Australia) have been analysed with a view to comparing their relative abundances of structurally similar hydrocarbons. The consistent relationships between hydrocarbons in crude oils that are chemically related via hydrogenation/dehydrogenation reactions suggest that a hydrogen exchange process similar to that demonstrated in laboratory experiments occurs during crude oil formation in sedimentary rocks.