中低煤阶高有机硫煤含硫结构演化特征

采用计算机曲线拟合方法对实验数据进行分峰处理,定量分析了9个中低煤阶高有机硫煤样的红外光谱(FT-IR)数据特征。研究表明,二硫醚与碳碳双键吸收峰面积比值(X₁)、硫醇与碳碳双键吸收峰面积比值(X₂)分别与R_max以及有机硫含量(S_o,d)呈显著的正相关性。煤质参数相近,有机硫含量及其占全硫比例受微环境的影响。同一煤样中,二硫醚、硫醇、二硫化铁三种含硫结构红外参数均依次递减。低煤阶及低-中阶烟煤阶段,以二硫醚、硫醇为代表的有机硫与含氧官能团的红外参数呈现此消彼长关系,且在第二次煤化跃变点附近,参数急剧增大。高有机硫煤样随煤阶升高,脂肪链支链化程度下降,芳构化程度加大,与一般低硫煤结构演化特征相符。      

泥炭藓煤热模拟系列二阶导数红外光谱研究

泥炭藓煤热模拟系列二阶导数红外光谱研究彭文世，陈德玉（中国科学院广州地球化学研究所．广州５１０６４０）关键词泥炭藓煤，热模拟，二阶导数红外光谱许多科学家曾用红外光谱技术研究过煤和干酪根的热演化问题：详细讨论了不同变质程度的煤和沥青的红外光谱［１］；利...     

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。      

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。      

次火山热质炮的物理测试特征

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＾Ｏ＝１．１０％时达最大值。顺磁共振自由其浓度和Ｘ－衍射参数Ｌａ／Ｌｃ介于区域变质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＾ｏ的演化。     

构造应力对煤化作用的影响及其瓦斯灾害性

通过对豫西滑动构造区二1煤动力变质作用特征的研究,探讨了构造煤变质成烃作用与煤化进程的应力影响因素。研究结果表明,不同性质的构造应力具有不同的煤化效应;与拉张应力相比,具各向异性的挤压应力,对煤变质程度的增加、煤基本结构单元BSU侧链和官能团的脱落,以及煤层瓦斯的生成,都具有很大的促进作用。      

利用镜质体芳核C=C键红外吸收波数的变化规律测定煤的变质程度

用ＩＲ－１６００系列傅利叶变换红外线分光光度计对腐植煤系列的褐煤、长焰煤、气煤、工、焦煤、瘦煤、贫煤和无烟煤煤样的镜质作了测定，共红外光谱特征反映了它们在变质程度上的区别。得出的镜质体芳核Ｃ＝Ｃ键红外吸收波数随煤级变化曲线，反映腐植煤的芳核Ｃ＝Ｃ键红外吸收波 随煤化程度增加而降低或向低波娄迁移的规律。有理由相信、腐植煤的煤化程度或牌号煤也可以用红我光谱方法精确确定。     

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。      

腐泥煤变质系列的红外光谱和X衍射特征

对淄博、滕县两煤田不同煤级与腐植煤共生的腐泥煤系列进行了对比研究。红外光谱特征为：反映芳环－Ｃ＝Ｃ－键伸缩和弯曲振动的１６００ｃｍ－１峰的吸收值都小于共生腐植煤；反映芳烃ＣＨ基团面外弯曲振动的８８０ｃｍ－１峰只在腐植煤中出现，而８１０ｃｍ－１峰的吸收值全部高于腐植煤；两次出现了在腐植煤中从未出现过的８１０ｃｍ－１＞７５０ｃｍ－１的情况；芳烃结构指数＞０８，而腐植煤则全部＜０８。Ｘ线衍射结果：ＬＣ都随煤化作用的进行逐渐增大，在Ｃｄａｆ为９２％±达峰值，然后又逐渐变小；两个系列相比，全都是腐泥煤较大；Ｌａ都随煤化作用的进行逐渐增大，大部分腐植煤比腐泥煤的大；ｄ（００２）都随煤化作用的进行逐渐变小，两个系列相比都是腐泥煤的较小。     

不同煤化程度煤热解过程中汞释放规律

采用热重与测汞仪联用技术,对5种不同煤化程度的煤进行氧化热解实验,研究不同煤化程度煤的热解过程及煤中汞的释放规律。结果表明:X射线衍射（XRD）曲线中衍射峰的特征可反应煤化程度,衍射峰的高度越高,宽度越窄,煤化程度就越高。不同煤化程度的煤在氧气中热解,质量损失随煤化程度的加深而增大,且随着煤化程度的加深,氧化热解的起始温度、最大热分解温度、终止温度也逐渐升高。随着煤化程度的升高,煤中汞释放所需的时间逐渐增加,且汞释放最大值所对应的热重（TG）曲线热解率最大的温度随煤化程度的加深而升高。      

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.     

煤变质作用研究

本文从4个方面扼要地讨论了煤变质作用的近期进展。在煤级参数方面对镜质体反射率及其缺点和弥补的方法做了介绍,简述了近来提出的新的煤级参数。在煤化作用机理与特点方面概述了涉及煤化作用的煤结构研究新进展及其在煤化过程的演变中与镜质体反射率、挥发份的内在联系;煤化作用跃变与沥青化作用;“惰性组的煤化径迹”——煤化作用的一个新的方面。新的煤变质作用类型探讨。煤变质因素和煤化作用平衡,煤变质作用研究应用于其它地质学科。最后提出了应进一步研究的煤变质问题。     

Application of reflectance micro-Fourier transform infrared analysis to the study of coal macerals: an example from the late jurassic to early cretaceous coals of the Mist Mountain Formation, British Columbia, Canada

The applicability of the reflectance micro-Fourier Transform infra-red spectroscopy (FTIR) technique for analyzing the distribution of functional groups in coal macerals is discussed. High quality of spectra, comparable to those obtained using other FTIR techniques (KBr pellet and transmission micro-FTIR), indicate this technique can be applied to characterizing functional groups under most conditions. The ease of sample preparation, the potential to analyze large intact samples, and ability to characterize organic matter in areas as small as 20 μm are the main advantages of reflectance micro-FTIR. The quantitative aspects of reflectance micro-FTIR require further study.The exaples from the coal seams of the Mist Mountain Formation, British Columbia show that at high volatile bituminous rank, reflectance micro-FTIR provides valuable information on the character of aliphatic chains of vitrinite and liptinite macerals. Because the character of aliphatic chains influences bond disassociation energies, such information is useful from a hydrocarbon generation viewpoint. In medium volatile bituminous coal liptinite macerals are usually not detectable but this technique can be used to study the degree of oxidation and reactivity of vitrinite and semifusinite.     

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.     

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.     

Chemometric analysis of functional groups in fossil remains of the Dicroidium flora (Cacheuta, Mendoza, Argentina): Implications for kerogen formation

Studied samples include eight Gondwanan species of the Dicroidium flora: seed ferns (3), conifer (1), cycad-related (1), unknown affinity gymnosperms (2), and one undetermined axis from two Middle to Upper Triassic localities (Cacheuta, Mendoza, central western Argentina). Based on differing preservation states and sample treatments, four sample forms are established: (1) compressions, (2) cuticles, (3) cuticle-free coalified layers, and (4) associated coal samples. The purpose of the study is firstly to analyze the sample forms using Fourier transform infrared (FTIR) spectrometry, contributing to filling an existing gap of chemical information for Gondwanan pant fossil remains. Secondly, semi-quantitative chemical parameters, calculated by area integration of infrared spectra, are treated using principal component analysis to infer statistical groupings as a function of chemical structures (functional groups). From the initial two-component solution, based on the 8 × 41 data matrix, a subset matrix (4 × 29) could be isolated which also yielded a two-component solution (in each case, cumulative explained variance is at least 89%). Results include the distinction between the coaly forms (1) compressions and (3) cuticle-free coalified layers mainly based on the carbonyl contents and branching and length of the hydrocarbon side chains. The highly aliphatic nature of cuticles, which is indicative of biomacromolecules (cutin), is noted. Similarities in functional groups are recorded with types of kerogen and coal macerals. The result enables us to postulate that the functional groups characterizing the different modes of preservation of our fossil remains are likely related to the propensity to generate oil and gas/condensate from the kerogen. Our data have the potential for future studies with implications for chemotaxonomy, molecular taphonomy, and paleoclimatology.     

构造煤与原生结构煤的热解成烃特征研究

通过对平顶山、郑州和南票3大矿区石炭二叠纪含煤岩系中高煤级烟煤和无烟煤的热解成烃潜力分析,探讨了构造煤热解产烃潜力与原生结构煤的不同演化特征及其影响因素。结果表明,构造应力,尤其是剪切应力对煤大分子聚合物的侧链及官能团,具有一定的降解能力,促进了成烃的演化速率。      

早期煤化作用机制与有机质早期成烃演化

近年来，未熟和低熟油气田的发现、生物气藏的勘探和开发，极大地促进了对有机质早期转变的研究；而有机质早期转变机制的正确认识对于煤和干酪根中显微组分的成因、后期热演化都有着重要的影响。对早期煤化作用机制和有机质早期成烃作用的研究现状、进展及存在的问题进行了综述。