南票热变煤中不溶有机质的谱学研究

通过对南票热变煤的Ⅰ·Ｒ、Ｒｏｃｋ—ｅｖａｌ与ＸＲＤ的研究，对其成煤母质、煤级、矿物与热变煤的物理化学结构演化等方面有了新的认识：该煤生成有低等生物参与；煤脱矿作用使脂肪结构优先低温氧化，煤中矿物对Ｓ２峰影响较大；Ｔｍａｘ、ＴＰＩ、ＯＰＩ、ｄ００２、Ｌｃ等为较好的成熟度参数，而ＨＩ、Ａ因子、Ｃ因子、脂芳比受成熟度与母质双重因素影响；ｄ００２、Ｌｃ与温度和有机质受热速度有关；镜质体反射率主要取决于稠环芳香结构规整程度；Ｌａ、Ｌｃ下降与Ｌａ／Ｌｃ＞１是热变煤特征；热变煤的物理化学结构演化类似区域变质煤。     

干酪根分子结构在低熟阶段的演化特征：基于红外光谱分析

为研究低熟气形成过程中大分子结构的变化情况,对吐哈盆地侏罗系八道湾组的煤与碳质泥岩干酪根在不同升温速率下进行了热解实验,借助于红外光谱分析,研究了不同热模拟温度下干酪根结构的特征与变化。结果表明,随热演化的进行,煤与碳质泥岩干酪根的芳香结构不断缩合,含氧官能团不断脱落,碳质泥岩干酪根中的脂肪族类有所降低。吐哈盆地低熟气主要来源于煤与碳质泥岩干酪根中的含氧官能团--羧基与甲氧基,以及碳质泥岩干酪根上的脂肪族。从干酪根结构上揭示了低熟气主要来源于Ⅲ型有机质的原因。     

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。     

南华北区两类不同还原型镜质组化学结构特征研究

采用博里叶红外光谱和Ｘ射线衍射分析方法，探讨了南华北区两类不同还原型镜质组化学结构物差异和随煤阶的变化。较强 原型镜质组明显比同煤阶较弱还原型镜质组含有较多的脂类结构，较少的芳环结构。随煤阶的增高，镜质组结构向芳环晶化程度增强的方向演变，芳香度、面网间距、晶核高度和宽度及芳环层数等结构参数均呈规律性变化。     

成烃理论的发展

世界上特别是中国未成熟石油的普遍存在，突破了干酪根热降解成烃的理论模式。研究表明，沉积岩中可溶和不溶有机质，是一个有机联系的整体，共同参与了油气的生成。在成岩作用阶段，干酪根不产烃，未成熟石油来自可溶类脂物的直接降解成烃作用；干酪根的热降解成烃作用主要发生在深成作用阶段早期（Ｒｏ＝０．５％～１．２％），产生正常原油；后期是以缩合焦沥青裂解产生高成熟轻质油及油裂解成气为主的湿气阶段（Ｒｏ＝１．２％～２．０％）。提出了一种新的可溶和不溶有机质共同参与成烃的演化模式     

有机显微组分X射线衍射分析方法在油气评价中的应用

Ｘ射线衍射分析法适宜于分析有机显微组分的芳环层的层状结构。有机质的芳环层结构与其类型和演化程度有关。表征有机质芳环层的层状结构的主要参数：高度Ｌｃ、宽度Ｌａ、网面间距ｄｈｋ１和芳环层层数可作为油气勘探中判断源岩性质、类型、演化程度与生烃潜力的依据。文章还对参数的变化与意义进行了初步讨论。     

冲绳海槽沉积物中酚类有机物色谱-质谱鉴定

作者从冲绳诲槽水深1000m的海底软泥中，分析出三种酚类有机物，海洋软泥有机质使用氯仿甲醇抽提、薄层色谱分离、气相色谱分析、色谱-质谱-数据系统联用仪鉴定，经定性的三种酚类有机物是：2-甲氧基-5-(1-丙烯基)酚；2-甲氧基-4-（2-丙烯基)酚；2，6-双(1，1-二甲基乙基）-4-甲基酚。     

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。     

中国东北干旱-半干旱地区湖泊沉积物木质素酚类化合物特征及其气候指示意义

木质素广泛分布于维管植物,经分解生成的酚类化合物可示踪有机质来源、评估木质素降解程度,进而用于反演古环境与古气候变化。采用合适的分析方法有效地分解木质素是推断母源植物类型、降解程度的技术基础,常规方法是木质素经碱(或酸)解后,利用气相色谱-质谱法(GC-MS)分析酚类单体化合物,但分解、提取过程复杂、易引入杂质。热裂解技术可在高温下快速分解有机质,裂解产物可通过GC-MS进行在线分析,具有用样量少、有机质提取比例高、重现性好、操作便捷的特点。本文选择地处亚洲夏季风影响区域的边缘的内蒙伊和沙日乌苏湖,采用热裂解GC-MS(Py-GC/MS)技术,对湖泊沉积物进行裂解分析,在对裂解温度(450℃、550℃和650℃)进行了优化的基础上,识别了21种酚类化合物,包括：4-甲基苯酚、2-乙基苯酚等9种烷基酚类(PHs),4-乙基-2-甲氧基苯酚、4-乙烯基-2,6-二甲氧基苯酚等9种烷基酚类(PHs)和12种甲氧基酚类(LGs)。结合沉积岩心样品AMS ¹⁴C年龄的分析结果,6.7ka以来沉积物中酚类化合物总量、PHs和LGs的变化趋势总体一致,呈现出6.7～4.0ka相...     

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。      

煤成烃生成及排驱加水热模拟实验

用加水热模拟实验对采于我国胜利油田附近的石炭系太原组亮褐煤（R0＝0．56%）生烃潜力进行研究。煤样富含镜质组（74．5%）,壳质组少（8．8%）,惰性组占16．7%,其中镜质组以富氢的基质镜质体为主。煤样裂隙发育,形成于滨海沼泽相沉积环境。实验设200℃、230℃、260℃、290℃、320℃和350℃六个温度点,每个温度点加热72小时。实验结果表明该煤具有较高的生烃潜力和排油效率。其液态烃大量生成和排出始于R0＝0．76%（290℃）,在R0＝1．18%（320℃）时达高峰。气态产物从R0＝1．18%大量形成,直到R0＝1．53%（350℃）继续增大。实验分析认为煤的生烃能力除了与其有机质类型、有机质丰度等有关外,还与其形成的沉积环境有关,缺氧的还原环境是煤作为烃源岩形成和保存的有利沉积环境。裂隙的发育有助于煤成油的排驱和运移。     

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.     

广西百色盆地州景矿第三系褐煤有机地球化学与煤岩学研究 Ⅳ．单化合物碳稳定同位素推断生物标志物起源

一个未成熟褐煤抽提物中，高等植物生源化合物的同位素值在全煤碳同位素组成（δ１３Ｃ值－２７．０‰）的±２‰范围内，表明相似成煤植物对这些化合物的贡献，或者其成煤植物经历过相似的生物合成分馏效应。所检测的萜烃类按同位素差异分为两组:二萜类（δ１３Ｃ值－２５．０±１．４‰）和倍半萜类（δ１３Ｃ值－２５．９±１．５‰）平均较全煤样富集１～２％。１３Ｃ，而奥利烷－乌散烷－羽扇烷型衍生物（δ１３Ｃ值－２９．０±０．８‰）平均比全煤样减少１～２‰１３Ｃ。Ｃ₁₅～Ｃ₃₅正烷烃δ１３Ｃ平均值－３２．４±０．６‰，据此表明Ｃ₁₇～Ｃ₂₂和Ｃ₂₂～Ｃ₃₃正烷烃的同位素值与上述平均值没有明显差异。与全煤样相比较，该煤样抽提物的藿烷衍生物１３Ｃ值则减少８～３４‰，标志在成煤过程中甲烷的细菌循环起着作用。     

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.     

A study of lignin degradation in leaf and needle litter using C-labelled tetramethylammonium hydroxide (TMAH) thermochemolysis: Comparison with CuO oxidation and van Soest methods

We studied the degradation of lignin in leaf and needle litter of ash, beech, maple, pine and spruce using ¹³C-labelled tetramethylammonium hydroxide (¹³C TMAH) thermochemolysis. Samples were allowed to decompose for 27 months in litter bags at a German spruce forest site, resulting in a range of mass loss from 26% (beech) to 58% (ash). In contrast to conventional unlabelled TMAH thermochemolysis, ¹³C-labelling allows thermochemolysis products from lignin, demethylated lignin and other polyphenolic litter compounds (e.g. tannins) to be distinguished. Proxies for lignin degradation (phenol yield; acid/aldehyde ratio of products) changed considerably upon correction for the contribution of non-lignin sources to the thermochemolysis products. Using the corrected values, we found increasing acid/aldehyde values as well as decreasing or constant yield of lignin derived phenols normalised to litter carbon, suggesting pronounced lignin degradation by wood-rotting fungi. No indication for build up of demethylated lignin through the action of brown rot fungi on ring methoxyls was found. The results were compared with those of other analytical techniques applied in previous studies. Like ¹³C-TMAH thermochemolysis, CuO oxidation showed increasing lignin oxidation (acid/aldehyde ratio) and no/little enrichment of lignin derived phenols in the litter. Molecular lignin degradation patterns did not match those from analysis of total acid unhydrolysable residues (AURs). In particular, the long assumed selective preservation of lignin during the first months of litter decomposition, based on AUR analysis, was not supported by results from the CuO and ¹³C TMAH methods.     

Formation of planetary systems and brown dwarfs around single stars

The conditions for the formation of planets and brown dwarfs around single main-sequence stars are considered in two scenarios. The formation of planets and brown dwarfs requires that the initial specific angular momentum of a solar-mass protostar be (0.32)×10¹⁸ cm²/s. The accreted matter of the protostar envelope forms a compact gas ring (disk) around the young star. If the viscosity of the matter in this ring (disk) is small, increasing its mass above a certain limit results in gravitational instability and the formation of a brown dwarf. If the viscosity of the gas is sufficiently large, the bulk of the protostar envelope material will be accreted by the young star, and the gas disk will grow considerably to the size of a protoplanetary dust disk due to the conservation of angular momentum. The formation of dust in the cool part of the extended disk and its subsequent collisional coalescence ultimately results in the formation of solar-type planetary systems.     

Petrographic and geochemical effects of sill intrusions on coal and their implications for gas outbursts in the Wolonghu Mine, Huaibei Coalfield, China

Since the early 1980s, fifteen outbursts have occurred in the Huaibei Coalfield of China. These outbursts were reported to be associated with sills. To study the effect of sill intrusions on coal seam and their relationship to methane outbursts, eleven samples from the No. 10 coal seam were taken from the Wolonghu Mine at various distances from a diorite sill. Comparisons were made between unaltered and heat-affected coals using petrographic and chemical data, micropore characteristics, adsorption properties of coal, and gas outburst indexes from field. Approaching the intrusion, vitrinite reflectance levels increased from 2.74% to 5.03%, and the thermal aureole of the sill ~ 60 m (from the sill boundary to sample 9). Three zones along this gradient were identified as corresponding to (1) thermal evolution zone No. 1 (0-5 m from sill), (2) thermal evolution zone No. 2 (5-60 m from sill), and (3) unaltered zone. The methane adsorption capacity of coal samples in the thermal evolution zone No. 2 was generally higher than in the two other zones, and the unaltered zone higher than the thermal evolution zone No. 1. It is concluded that the contact-metamorphism decreased the adsorption capacity of coal and the thermal evolution of sill increased it. The trap effect of sill, combined with the mudstone and siltstone roof and floor of the No. 10 coal seam, provided a seal for the formation of a gas pocket. Abnormally high formation pressures at the No. 10 coal seam led to two outbursts.     

平朔露天煤矿复垦区土壤中多环芳烃分布特征、来源解析及风险分析

原煤的开采、储存、运输及其加工利用过程是多环芳烃(PAHs)污染的主要来源。由于缺乏相关系统调查数据,其对煤矿复垦区土壤环境质量的影响尚不明确。平朔煤矿复垦土地主要作为耕地利用,了解其PAHs污染状况直接关系粮食安全和人体健康。该研究通过野外实地调查,开展了平朔煤矿复垦区表层土壤中多环芳烃(PAHs)的毒性风险分析研究。在整个平朔煤矿45 km2范围内,以500 m×500 m间距为基准,按照不同用地类型,采集了0~20 cm深度土壤样品179个,再按照1 km×1 km单元格组合后分析。使用安捷伦高分辨气相色谱低分辨质谱进行目标物的检测。加入代用标准2氟联苯(2 FBP)以进行回收率控制。研究结果表明：土壤中16种EPA PAHs的含量范围为213.60~2 513.20 ng·g-1,均值为717.09 ng·g-1。PAHs成分特征显示主要以3~4环为主(52%),5~6环次之(42%),2环所占比例最低(6%)。使用相关分析法判定,主要污染来源为原煤。毒性风险分析结果显示,平朔煤矿土壤PAHs存在一定生态风险,当土地重新作为农田加以利用时,需要加以关注。     

A study of the effect of igneous intrusions on the structure of an Australian high voltage bituminous coal

Samples of heat affected coal taken near two igneous intrusions (dykes) in the Victoria Tunnel Seam of the Newcastle Coalfield have been investigated by chemical analysis, petrography, Fourier transform infrared spectroscopy and solid state¹³C NMR spectroscopy. Visual inspection of the seam near the intrusion showed four distinct zones. These have been called, in order of increasing distance from the dyke, the massive cinder, the banded cinder, heat affected coal and apparently unaffected coal. The samples show an increase in structural change as the distance from the dyke decreases, with the samples taken from the massive cinder nearest the dyke being classified as semicokes.FTIR and¹³C NMR results, together with the results of dipolar dephasing NMR experiments, suggest that the predominant structural change in the heat affected zone is replacement of aromatic ethers and/or phenols with hydrogen, leading to an increase in proton aromaticity. Closer to the intrusion, bond rupture leads to a marked loss of aliphatic groups, while in the most affected region adjacent to the dyke aromatic crosslinking has also occurred to form coke-like material.