Early maturation processes in coal. Part 1: Pyrolysis mass balance and structural evolution of coalified wood from the Morwell Brown Coal seam

We have developed a theoretical approach for evaluating the maturation of kerogen-like material, involving molecular dynamic reactive modelling with a reactive force field to simulate thermal stress. Morwell Brown Coal was selected to study the thermal evolution of terrestrial organic matter (OM). To achieve this, a structural model is first constructed on the basis of literature models and analytical characterization of our samples using modern 1and 2D nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy and elemental analysis. Then, artificial maturation of the coal is performed at low conversion in order to obtain quantitative and qualitative detailed evidence for the structural evolution of the kerogen upon maturation. The chemical changes include defunctionalization of carboxyl, carbonyl and methoxy functional groups, coupled with an increase in cross linking in the residual matured kerogen. Gaseous and liquid hydrocarbons, essentially CH₄, C₄H₈ and C₁₄₊ hydrocarbons, are generated in low amount, merely via cleavage of the lignin side chain.     

Thermal decomposition process in algaenan of Botryococcus braunii race L. Part 2: Molecular dynamics simulations using the ReaxFF reactive force field

This paper reports ReaxFF MD simulation results on pyrolysis of a molecular model of the algaenan Botryococcus braunii race L biopolymer, specifically, ReaxFF predictions on the pyrolysis of prototypical chemical structures involving aliphatic chain esters and aldehydes. These preliminary computational experiments are then used to analyze the thermal cracking process within algaenan race L biopolymers. The simulations indicate that the thermal decomposition of the algaenan biopolymer is initiated by the cleavage of a C–O bond in the ester group, followed by the release of carbon dioxide. We also observe a significant, strongly temperature dependent, release of ethylene. This degradation mechanism leads to products similar to those observed in pyrolysis experiments, validating this computational approach.     

Chemical structural models for coalified wood (vitrinite) in low rank coal

Examination of a series of coalified gymnospermous woods ranging in rank from brown coal to subbituminous coal by solid-state ¹³C NMR and analytical pyrolysis has provided sufficient information to construct structural models depicting the changes that occur to lignin, the primary precursor of vitrinite, during coalification. Progressive changes in the chemistry of coalified wood suggest the following series of reactions: (1) demethylation to form catechol-like structures that are dominant components of brown coal and lignite A; (2) cleavage of aryl ether linkages to form phenols and reactive carbocations that alkylate the catechol rings; (3) dehydration of the catechol rings; (3) dehydration of the catechol-like structures to form the structures of subbituminous coal dominated by alkylphenols; and (4) reduction of the 3-carbon alkyl side chain derived from lignin to form propyl substituents. The models developed for each stage of coalification are derived from chemical modifications of the structure of lignin.     

Nuclear magnetic resonance studies of ancient buried wood—II. Observations on the origin of coal from lignite to bituminous coal

Coalified logs ranging in age from Late Pennsylvania to Miocene and in rank from lignite B to bituminous coal were analyzed by ¹³C nuclear magnetic resonance (NMR) utilizing the cross-polarization, magic-angle spinning technique, as well as by infrared spectroscopy. The results of this study indicate that at least three major stages of coalification can be observed as wood gradually undergoes transformation to bituminous coal. The first stage involves hydrolysis and loss of cellulose from wood with retention and differential concentration of the resistant lignin. The second stage involves conversion of the lignin residues directly to coalified wood of lignitic rank, during which the oxygen content of intermediate diagenetic products remains constant as the hydrogen content and the carbon content increases. These changes are thought to involve loss of methoxyl groups, water, and C₃ side chains from the lignin. In the third major stage of coalification, the coalified wood increases in rank to subbituminous and bituminous coal; during this stage the oxygen content decreases, hydrogen remains constant, and the carbon content increases. These changes are thought to result from loss of soluble humic acids that are rich in oxygen and that are mobilized during compaction and dewatering. Relatively resistant resinous substances are differentially concentrated in the coal during this stage. The hypothesis that humic acids are formed as mobile by-products of the coalification of lignin and function only as vehicles for removal of oxygen represents a dramatic departure from commonly accepted views that they are relatively low-molecular-weight intermediates formed during the degradation of lignin that then condense to form high-molecular-weight coal structures.     

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。     

Study of petroleum generation by pyrolysis—I. Pyrolysis experiments by Rock-Eval and assumption of molecular structural change of kerogen using13C-NMR

Green River shale (Type I kerogen), Yaamba shale (Type II kerogen) and Sarufutsu coal (Type III kerogen) were heated to various temperatures using Rock-Eval. The amount of hydrocarbons generated and weight loss by pyrolysis were measured to obtain a better understanding of petroleum generation. After the pyrolysis experiments, elemental analysis (C, H), vitrinite reflectance (%R_o) measurement, maceral observation, infrared spectroscopy (IR) and¹³C-NMR spectroscopy were carried out on the coal samples. Changes in H/C atomic ratio, IR and NMR spectra indicate that experiments by Rock-Eval resemble those of the natural evolution of kerogen. However, the petrographic changes of the coal show more similarity to coal liquefaction and coking than to natural coalification. Changes in the amount of generated hydrocarbons with increasing maturation show that Type II kerogen produces more hydrocarbons than does Type I when R_o does not exceed 1.1%. Petroleum generation curves for the three samples were concordant with trends in natural systems, and a conceptual model of petroleum generation curve classified into three types is proposed, namely (1) curve of total amount enerated, (2) curve of generation rate, and (3) curve of fluid composition. Changes of IR and NMR spectra after pyrolysis imply that generated hydrocarbons are derived from aliphatic C structures of kerogen macromolecules. Moreover, the difference in genetic potential between Type I and Type III reflects different amounts of aliphatic structures. Type I is assumed to have a simple assemblage (mainly polymethylene carbons), and Type III is assumed to have a more complex variety of structures that are responsible for the difference in generation rates between the two kerogen Types. A quantitative analysis of C species of various bond structure by¹³C-NMR confirms that petroleum generation is the process of bond cleavage of kerogen macromolecules; lower-energy bonds decrease at an earlier stage of reaction, while aromatic carbons with higher bond energies survive to form graphitic structure at postmature stages. Emphasis is placed on the idea that the most important and direct factor in petroleum generation is a change in the molecular structure of kerogen with increasing maturation. NMR and other methods providing information about molecular structures of kerogen will become strong tools for evaluating source rocks and sedimentary basins in the future.     

Gelification of Victorian tertiary soft brown coal wood. I. Relationship between chemical composition and microscopic appearance and variation in the degree of gelification

The relationship between chemical composition and microscopic appearance of present-day wood-derived materials and Victorian xylites and gelified soft brown coal woods, Latrobe Valley, Australia, is discussed. The present-day wood-derived material consists of milled wood and lignin and holocellulose fractions prepared from an angiosperm, Eucalyptus regnans and a gymnosperm, Pinus radiata. The xylites and least gelified soft brown coal woods resemble the P. radiata lignin fraction; the latter contains residual cellulose.The atomic H/C ratio was found to be a useful guide to the degree of gelification. Increase in the degree of gelification was accompanied not only by an increase in the total huminite reflectance, but also by an increase in the reflectance of the individual huminite submacerals. The loss of hymotelinite autofluorescence under ultraviolet and blue light excitation with increase in the degree of gelification of Victorian soft brown coal woods was ascribed primarily to the elimination of cellulose and, possibly, modification of the lignin structure of xylite.     

Degradation of native wheat straw lignin by Streptomyces viridosporus T7A

Lignin is one of the major contributing factors toward the recalcitrance of lignocellulosic biomass. Understanding the process of lignin degradation in natural biological processes will provide useful information to develop novel biomass conversion technologies. Functional group changes in the lignin entities during the process may contribute to the cellulose degradation (utilization) by the microorganisms. In this study, compositional and advanced Fourier transform infrared, pyrolysis gas chromatography/mass spectrometry and ¹³C cross polarization/magic angle spinning nuclear magnetic resonance analysis were performed to explore the mechanism of biodegradation of wheat straw by Streptomyces viridosporus T7A. The results indicated that S. viridosporus T7A removed lignin and hemicelluloses as indicated by the increased carbohydrate/lignin ratio. Significant modification of carbonyl and methoxyl groups in the complex lignin structure was also evident. Most importantly, the quantitative results showed that lignin degradation was featured by deduction of guaiacyl unit. The results provide new insight for understanding lignin degradation by bacteria.     

Maturity Control on the Patterns of Hydrocarbon Regeneration from Coal

Rock-Eval pyrolysis and Py-GC experiments on naturally and artificially matured coal samples were carried out. The results suggest that both depolymerization and defuctionalization exist during the maturation and evolution of coal. The patterns of hydrocarbon regeneration are diverse at different stages of the maturation and evolution. When the vitrinite reflectance (R0) is 0.7%-0.9%, bitumen is the richest in coal while activation energy is the minimum, and the temperature of peak yield is lower than that of primary hydrocarbon generation. However, if reflectance is greater than 0.9%, defunctionalization predominates and the temperature of peak regeneration is shown in lagging compared with the primary hydrocarbon generation. When reflectance is out of the "oil window", the peak temperature of hydrocarbon regeneration and that of the primary hydrocarbon generation seems to be continuous.     

Sorption characteristics and mechanisms of ammonium by coal by-products: slag, honeycomb-cinder and coal gangue

The adsorption behaviors of ammonium from aqueous solutions were investigated for three solid coal wastes, slag, honeycomb-cinder and coal gangue. The ammonium sorption processes were well modeled by the pseudo second-order model (R ² > 0.99). The experimental data were fitted to both the Langmuir model and the Freundlich model, with the Langmuir model better representing the data. The maximum ammonium sorption capacities calculated from the Langmuir model were 3.1, 5.0 and 6.0 mg/g for the slag, honeycomb-cinder and coal gangue samples, respectively. The pH value of the solution affected the ammonium removal, and the higher uptakes found in either neutral or alkaline conditions for the three materials. The thermodynamic parameters, ΔH, were calculated to be 29.75, 25.21 and 17.91 kJ/mol for the SL, HC and CG samples, respectively, with the positive values indicating that the ammonium sorption processes were endothermic. Based on the results, it can be concluded that coal gangue may have more potential for being used as a sorbent for the ammonium removal from wastewater among the three coal by-products.     

Can pyrolysis-GC/MS be used to estimate the degree of thermal alteration of black carbon?

Very little is known about the macromolecular properties of biomass combustion residues referred to as black carbon (BC). Pyrolysis-gas chromatography–mass spectrometry (Py-GC/MS) was performed on: (i) peat from Spain at 400–1200 °C to investigate the effect of charring on pyrolysis fingerprint and (ii) natural charcoal from Laos in order to link molecular information to published chemical and reactivity parameters. Confirming earlier Py-GC/MS studies, the BC in the artificially charred peat and the natural charcoal produced predominantly benzene, toluene, C₂-benzenes, PAHs and benzonitriles. Furthermore, some charcoal samples produced significant amounts of phenols, methoxyphenols, carbohydrate markers, n-alkanes and n-alkenes upon pyrolysis, reflecting non-charred and weakly charred biomass. A series of pyrolysis product ratios related to the degree of dealkylation of the pyrolysis products (benzene/toluene, naphthalene/C₁-naphthalenes, C₁-naphthalenes/C₂-naphthalenes, benzofuran/C₁-benzofurans and benzonitrile/C₁-benzonitrile) increased with increasing artificial charring (peat) and, for the natural charcoal, these ratios were in accordance with established chemical and reactivity parameters related to charring intensity from other methods: proportion of aromatic C obtained from solid state ¹³C nuclear magnetic resonance spectroscopy (NMR), the proportion of charred material as estimated from NMR in conjunction with a molecular mixing model (NMR–MMM) and the resistance to acid dichromate oxidation. The alkyl side chains of aromatic pyrolysis products are probably inherited from short chain aliphatic C chains that cross link the predominantly aromatic building blocks of BC, and these linkages seem to disappear with increasing charring intensity. Thus, the degree of thermal alteration of BC can be discerned from the pyrolysis fragmentation pattern.     

Temperature and time effect on the concentrations of free radicals in coal: Evidence from laboratory pyrolysis experiments

The relationships between free radical concentration (N_g) and vitrinite reflectance (%R_o) of coal were tested through 36 laboratory anhydrous pyrolysis experiments. The experiments were carried out at isothermal reactor with pyrolysis temperatures ranging from 300 to 550 °C over 30–480 min. The effects of temperature and retention time on the N_g were investigated. The concentrations of free radicals in pyrolysis coal samples increase with increasing time and temperature of experiments and reach a maximum value at about 1.75 %R_o, and then decrease with further maturation. The Temperature Time Index (TTI) integral equation was applied to establish the relationship between the TTI and N_g in this paper. As the free radical concentration in organic matter is strongly maturity dependent, it may prove to be a valuable geothermometer for paleogeotemperature study in sedimentary basins.     

Hydrocarbon generation from coal,extracted coal and bitumen rich coal in confined pyrolysis experiments

Three sets of pyrolysis experiments were performed on extracted coal (R_o% 0.39), coal (initial bitumen 13.5 mg/g coal) and bitumen enriched coal (total bitumen 80.9 mg/g coal) at two heating rates of 2 °C/h and 20 °C/h in confined systems (gold capsules). For all three experiments, the yields of bitumen, Σn-C₈₊, aromatic components and ΣC_2–5 at first increase and then decrease with increasing EASY%R_o and reach the highest values within the EASY%R_o ranges of 0.67–1.08, 1.07–1.19, 1.46–1.79 and 1.46–1.68, respectively. In contrast, C₁/ΣC_1–5 ratio at first decreases and then increases with EASY%R_o and reaches a minimum value in EASY%R_o range of 0.86–1.08, closely corresponding to the maximum values of the yields of bitumen and Σn-C₈₊. Methane yields increase consistently with EASY%R_o. Nearly half of the maximum yield of methane from kerogen was generated at EASY%R_o > 2.2. The differences in methane yields among the three experiments at the same thermal stress are relatively minor at EASY%R_o < 2.2, but are greater with thermal stress at EASY%R_o > 2.2. This demonstrates that the kerogen always retained relatively more hydrogen and hydrocarbon generative potential at the postmature stage of bitumen rich coal than the extracted coal or coal.The maximum yield of ethane is 20–25% higher in the bitumen rich coal experiment than the extracted coal or coal, while the maximum yields of C₃, C₄ and C₅ in the former are double to triple those in the latter. This result demonstrates that the added bitumen in bitumen rich coal substantially increased the generation of these wet gases. However, the averaged values of activation energies (with the same frequency factors) for both the generation and cracking of individual wet gases are similar and do not show consistent trends among the three experiments. For all three experiments, activation energies for the generation and cracking of wet gases are significantly lower than those in previously published oil pyrolysis experiments with same frequency factors (Pan et al., 2012; Organic Geochemistry 45, 29–47). Methane δ¹³C values at the maximum temperature or EASY%R_o are close to those of initial wet gases, especially C₃, implying that the major part of methane shared a common initial precursor with wet gases, i.e., free and bound liquid alkanes.     

Characteristics and origins of coal cleat: A review

Cleats are natural opening-mode fractures in coal beds. They account for most of the permeability and much of the porosity of coalbed gas reservoirs and can have a significant effect on the success of engineering procedures such as cavity stimulations. Because permeability and stimulation success are commonly limiting factors in gas well performance, knowledge of cleat characteristics and origins is essential for successful exploration and production. Although the coal–cleat literature spans at least 160 years, mining issues have been the principal focus, and quantitative data are almost exclusively limited to orientation and spacing information. Few data are available on apertures, heights, lengths, connectivity, and the relation of cleat formation to diagenesis, characteristics that are critical to permeability. Moreover, recent studies of cleat orientation patterns and fracture style suggest that new investigations of even these well-studied parameters can yield insight into coal permeability. More effective predictions of cleat patterns will come from advances in understanding cleat origins. Although cleat formation has been speculatively attributed to diagenetic and/or tectonic processes, a viable mechanical process for creating cleats has yet to be demonstrated. Progress in this area may come from recent developments in fracture mechanics and in coal geochemistry.     

中国西北侏罗纪煤系显微组分热解油生物标志物特征及其意义

从西北地区侏罗纪煤中分离出来的不同显微组分热解油生物标志物总体上比较相似,但在一些特殊生物标志物的分布上存在明显差异。藻类体、孢子体、角质体热解油Pr/Ph比值一般在1.5～2.0之间,镜质体和基质镜质体热解油Pr/Ph比值在3～4之间,但均只有相应原煤抽提物Pr/Ph比值的一半。在常规生物标志物甾烷和萜烷组成中,藻类体和孢子体含有相对丰富的C27甾烷,角质体其次,镜质体和基质镜质体C27甾烷含量很低或者基本不含C27甾烷;藻类体和角质体含有较高的伽马蜡烷,而与藻类体来自相同原煤的孢子体伽马蜡烷含量很低;镜质体和基质镜质体基本上不含伽马蜡烷;分离显微组分的原煤伽马蜡烷含量均很低。由此可见,伽马蜡烷的含量不仅与有机质沉积水体的盐度有关,与母源的成分也有关系。显微组分热解油与煤系原油生物标志物组成特征对比表明,煤系原油是藻类体、孢子体、角质体等富氢组分和相对贫氢的镜质组生成产物的混合物。不同油气藏中的原油,每一类显微组分的贡献可能不尽相同,有些原油可能主要来源于藻类体和孢子体等富氢显微组分,而有些原油除了富氢显微组分有贡献外,镜质组对其也有一定的贡献,但富氢显微组分应该是煤系含油气盆地中主要的生油显微组分。     

煤地质学研究进展与前沿

煤地质学是以煤的形成、组成、煤系伴生矿产、煤层瓦斯和煤层气为主要研究内容的地质学分支。近年来随着我国和世界对煤炭资源安全开采、洁净利用的要求逐渐提高,煤及煤层气资源的勘探与开发,煤地质学的研究重点也在逐渐发生变化。通过分析2011-2015年《国际煤地质学》杂志发表的717篇学术论文,总结了近期煤地质学最新的研究热点与前沿。研究发现:煤层气资源评价以及与煤层气开发关系最为紧密的煤储层物性研究是各国煤地质科技工作者最为关注的热点;煤中的矿物质和元素地球化学一直为人们所重视;与煤的形成、开采和利用相关的煤岩学及有机地球化学,煤的自燃、燃烧与环境,沉积环境与煤炭演化,地理信息系统与矿区环境监测,矿井瓦斯,矿井构造,矿井水和煤的热解等方面的研究一直在持续开展;页岩气资源评价与开发越来越受到人们重视。      

煤热解气体主产物及热解动力学分析

为了研究不同煤化程度煤的热解气相产物、热解动力参数,采用热重-红外光谱-质谱（TG-IR-MS）联用技术对4种不同热演化程度的煤进行了热解实验。实时记录了4种煤样在30~1 100℃、10/min℃升温速率、氦气气氛下热解过程中释放的各种气体成分及其释放量的变化趋势。研究结果表明,随煤热演化程度升高,煤的失重率和最大失重速率逐渐降低,与煤的干燥无灰基挥发分呈正相关关系;随着热解温度的升高,煤中逐渐释放出水、甲烷、二氧化碳、氢气和二氧化硫等小分子气体,且随着煤化程度的升高,各种气体的释放峰逐渐向高温处偏移,说明煤的热稳定性逐渐升高。不同变质程度煤的热解动力学分析结果表明,随着煤变质程度增高,其活化能逐渐降低,说明其热效应强度和发生热解反应的能力在逐渐降低。      

Identification of ionene and other carotenoid degradation products from the pyrolysis of sporopollenins derived from some pollen exines,a spore coal and the Green River shale

Examination of the pyrolysis products of sporopollenins from Pinus montana, Picea canadensis and Fagus sylvatica pollen, a spore coal and the Green River shale kerogen has shown the presence of typical carotenoid degradation products, including especially ionene and various naphthalenes and hydro naphthalenes. The products are compared with similar materials obtained from β-carotene and its oxidative co-polymer and the mechanism of formation of the compounds is discussed.     

淮北煤田祁东煤矿煤和瓦斯中稳定碳同位素分布特征及其地质成因

对淮北煤田祁东煤矿6个煤层的24个煤样和12个气样的稳定有机碳同位素分析,分别研究了煤和瓦斯中碳同位素的分布特征和变化趋势,为不同煤层及瓦斯源分析提供理论依据。研究表明:祁东煤矿煤的δ13C为-25.11‰~-22.76‰,6-1煤层至9煤层碳同位素均值呈波动变化,可能受当时成煤时期沉积环境的影响;瓦斯的δ13C₁为-63.65‰~-52.51‰,表现出次生生物成因气的变化特征,二氧化碳碳同位素特征（-22.61‰~-17.96‰）表明其均是煤热解而来。      

Mercury in coal and the impact of coal quality on mercury emissions from combustion systems

The proportion of Hg in coal feedstock that is emitted by stack gases of utility power stations is a complex function of coal chemistry and properties, combustion conditions, and the positioning and type of air pollution control devices employed. Mercury in bituminous coal is found primarily within Fe-sulfides, whereas lower rank coal tends to have a greater proportion of organic-bound Hg. Preparation of bituminous coal to reduce S generally reduces input Hg relative to in-ground concentrations, but the amount of this reduction varies according to the fraction of Hg in sulfides and the efficiency of sulfide removal. The mode of occurrence of Hg in coal does not directly affect the speciation of Hg in the combustion flue gas. However, other constituents in the coal, notably Cl and S, and the combustion characteristics of the coal, influence the species of Hg that are formed in the flue gas and enter air pollution control devices. The formation of gaseous oxidized Hg or particulate-bound Hg occurs post-combustion; these forms of Hg can be in part captured in the air pollution control devices that exist on coal-fired boilers, without modification. For a given coal type, the capture efficiency of Hg by pollution control systems varies according to type of device and the conditions of its deployment. For bituminous coal, on average, more than 60% of Hg in flue gas is captured by fabric filter (FF) and flue-gas desulfurization (FGD) systems. Key variables affecting performance for Hg control include Cl and S content of the coal, the positioning (hot side vs. cold side) of the system, and the amount of unburned C in coal ash. Knowledge of coal quality parameters and their effect on the performance of air pollution control devices allows optimization of Hg capture co-benefit.