Nitrogen in Chinese coals

Three hundred and six coal samples were taken from main coal mines of twenty-six provinces,autonomous regions,and municipalities in China,according to the resource distribution and coal-forming periods as well as the coal ranks and coal yields.Nitrogen was determined by using the Kjeldahl method at U.S.Geological Survey(USGS),which exhibit a normal frequency distribution.The nitrogen contents of over 90% Chinese coal vary from 0.52% to 1.41% and the average nitrogen content is recommended to be 0.98%.Nitrogen in coal exists primarily in organic form.There is a slight positive relationship between nitrogen content and coal ranking.     

中国煤中氮同位素组成特征初步研究

本文采用Dumas燃烧法测定了部分中国煤样的氮同位素组成(δ~(15 )N),并结合文献数据和煤样品的地质背景初步探讨了影响煤中氮同位素组成的因素。研究表明:(1)中国煤的δ~(15 )N值介于+1.4‰~+5.1‰之间,与世界其他地区煤的δ~(15 )N值范围(+0.3‰~+5.4‰)相吻合;同一煤层剖面分层煤样(煤级相似)的δ~(15 )N值具有非均质性特征,最大可达2.5‰。(2)煤的δ~(15 )N值是煤变质作用、沉积环境等多种因素耦合作用的结果。变质作用对煤的δ~(15 )N值的影响主要包括原始煤级、变质程度(煤级)和煤变质作用类型;沉积环境对煤的δ~(15 )N值的影响包括成煤植物的氮源以及沼泽介质的物理化学条件和微生物活动性等因素。(3)就煤变质作用(煤级)而言,中国煤的δ~(15 )N值随煤级升高呈现增高的趋势,到无烟煤又有所降低,这是煤中氮同位素稳定性差异的结果。在高级烟煤阶段(贫瘦煤)之前,随煤级升高稳定性较差的14 N优先脱除,δ~(15 )N值增高,增高幅度约1‰。在高级烟煤至初级无烟煤阶段,煤中剩余的14 N已趋于稳定,随煤级升高,部分不稳定15 N优先脱除,δ~(15 )N值降低。在无烟煤阶段,随煤级升高,14 N和15 N同步脱除,δ~(15 )N值几乎不变。在不考虑含氮地质流体影响的情况下,深成变质作用和接触变质作用对煤中δ~(15 )N值的影响应相似。(4)就沉积环境而言,形成于海陆过渡相的中高硫煤/高硫煤的δ~(15 )N值最高,形成于陆相的特低硫煤和低硫煤的δ~(15 )N值次之,而形成于碳酸盐岩台地相的超高有机硫煤的δ~(15 )N值最低,这主要与沉积环境中成煤植物的氮源以及泥炭化作用阶段植物有机质降解程度的差异有关。一般以富集15 N的海水硝酸盐为氮源的成煤植物形成的煤(海陆过渡相中高硫煤/高硫煤)较以相对亏损15 N的大气氮为氮源的成煤植物形成的煤(陆相特低硫煤和低硫煤)要富集15 N。当成煤母质在泥炭化作用阶段受到微生物降解作用较弱时(陆相特低硫煤和低硫煤),形成的煤氮含量较高,δ~(15 )N会有所上升;当成煤母质在泥炭化作用阶段受到强烈的微生物降解作用时(碳酸盐岩台地相超高有机硫煤)成煤植物蛋白质(富15 N)被降解损失的较多,形成煤的氮含量较低,δ~(15 )N值又会有所降低。此外,煤的δ~(15 )N值还与惰质组含量有关,因为在丝炭化过程中大量损失氮使得惰质组的δ~(15 )N值偏低,当成煤母质遭受的降解作用较弱时(四台煤矿12号特低硫煤),惰质组含量变化对煤δ~(15 )N值的控制作用尤为明显。(5)就成煤时代而言,中国的晚古生代煤与中生代煤的δ~(15 )N值相近,都高于新生代煤的δ~(15 )N值。δ~(15 )N值的这种差异并不是因为不同成煤时代的成煤植物不同造成的,而是因为新生代煤样为尚未经历煤变质作用的褐煤,其氮损失较少,所以新生代褐煤δ~(15 )N值较低。     

邯郸-峰峰矿区不同变质程度煤中有机氮的赋存形态

氮是煤中的常见元素之一,煤中氮的赋存形态多样且随煤阶发生变化。以邯郸-峰峰矿区为例,利用X射线光电子能谱（XPS）实验,研究不同变质程度煤（R_ran=1.08%~3.67%）中有机氮的赋存形态,探讨煤中各形态有机氮相对含量随煤阶的变化规律。结果表明：按N 1s XPS谱图分峰峰值的结合能可将煤中氮的形态归为N-6、N-5、N-Q和N-X四种;研究区煤中N-5的相对含量最高,且随着煤阶的增高而降低;N-Q的相对含量随着煤阶的增高而增高;煤中N-6的相对含量随煤阶呈“增-减-稳”的变化规律;N-X的相对含量为9.1%~35.1%,其与煤阶关系不明显;在煤阶R_ran=1.08%~1.47%的范围内,煤的N 1s XPS谱图中缺失N-Q分峰,表明褐煤中相对含量最高的质子化吡啶氮在此阶段已几乎全部去质子化而转化为吡啶氮。不同变质阶段氮的赋存形态变化特征对燃煤发电及煤化工领域煤化学参数选取提供参考。     

中国煤中有机硫的分布及其成因

对来自全国26个省、市、自治区的290个煤样中有机硫的质量分数测试及研究,发现煤中有机硫质量分数基本分布在0%¹.0%范围内。在低硫煤中硫分以有机硫为主,在高硫煤中以无机硫为主。中、高硫煤中,广西、湖南等地区很大一部分煤中硫分以有机硫为主。在所采集的样品中,高有机硫煤(有机硫>1%)均分布在华南、华北两大聚煤区,属于石炭、二叠纪煤。高有机硫煤中有机硫质量分数的变化与变质程度无明显关系。煤炭形成过程中海水作用的影响,是导致煤中有机硫含量偏高的最主要原因。     

Striking liptinitic bark remains peculiar to some Late Permian Chinese coals

An unusual liptinite coal component has been reported in the Chinese literature over the past sixty years. It has been described as a maceral in the Chinese National Standard (1991), but it has not been named internationally. In Chinese literature it is called “barkinite”, on the basis of its morphological features and because it is believed to have originated as bark tissue.“Barkinite” occurs in Late Permian, marine-influenced coals and is best represented in the Changguang, Leping and Shuicheng Basins of southern China.The material originates from plant periderm or the bark of higher plants. However, “bark” contains a variety of substances, including resin and suberin, which are recognised as the precursors of the resinite and suberinite macerals. “Barkinite” is distinguished by (i) its thickness; individual pieces can be more than ten cells thick and several centimetres long and (ii) it fluoresces strongly at 0.6% vitrinite reflectance and loses its fluorescence at about 1.1% vitrinite reflectance.The reporting of “barkinite” from only Chinese coals may be due to its origin from Lepidodendron and Psaronius flora, which was common in the Northern Hemisphere during the Carboniferous, but which was isolated to China by the Late Permian. It is proposed that the remnant flora evolved into unique forms in China by the Late Permian. Lepidodendron and Psaronius remains, coupled with a strongly marine-influenced, peat-forming environment have given rise to “barkinite” and to its restricted distribution.     

生油煤形成的环境制约

通过对不同沉积环境下形成煤系源岩生烃潜力的对比研究，揭示出成煤古环境对煤成烃生成具有控制作用，并根据煤系源岩中赋存大分子有机质裂解产物分子的组成特征，提出了识别有利成烃煤相的分子有机地球化学方法——氢指数-苯酚/辛烷图解判识法。结果表明，沼泽环境覆水越深，煤中有机质富氢程度越高，生油气性能越好，裂解产物表现为正构烷烃和正构烯烃相对含量增加，以低本酚/辛烷值和高氢指数为特征；反之，沼泽环境覆水越浅，煤中有机质氢含量越低，裂解产物以高含量酚类化合物和芳香烃为特征，生油气性能关。由此表明，覆水型沼泽应是煤在烃，特别是煤成油生成的有利相带。     

晋东南和豫中地区煤矸石中氮及其环境效应

通过对晋东南和豫中地区几个煤矿矸石堆及其周围的土壤和水体、井下矸石取样分析,发现这些矿的煤矸石中全氮的背景值为0.4%~0.8%。在中高煤变质程度地区,含铵伊利石夹矸中全氮高达1.0%~1.6%,铵伊利石的存在对于矸石堆中全氮含量的提高具有贡献。在矸石山周围积水中,具有较高的氮含量,说明雨水比较容易从矸石堆中将氮淋滤出来。煤矸石堆周围土壤中的氮含量并不高,说明煤矸石淋滤物并没有发生明显的横向迁移,可能主要表现为垂向渗透,有可能对地下水造成潜在的氮污染。     

煤中剪切指向标志的类型讨论

通过与岩石中的剪切指向标志对比,初步研究了煤中的剪切指向标志。发现了如羽状脉体等特殊的指向标志。煤中剪切指向标志研究,是岩层构造运动学分析的主要内容,可判别局部剪应力方向,进而为确定应力场提供依据。     

Strenes and triterpenes in brown coals

The method of gas chromatography-mass spectrometry was used to identify rearranged 24-methylcholestenes, 24-ethylcholestenes and isohopene in brown coals. Possible routes and sources of formation of these hydrocarbons in nature are discussed. Mass spectra both of original hydrocarbons and of their saturated analogues are given.     

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.     

哈素海沉积物中氮和有机质的分布特征

针对哈素海富营养化日趋严重的现实,系统开展了湖泊沉积物中不同形态氮及有机质的空间分布和污染特征研究。结果表明,表层沉积物中TN、Org N、NH+4 N及有机质的水平分布均表现经向分异特征,Org N的分布特征主导了TN的水平分布格局,有机质与TN具有强相关性。沉积柱芯中TN随深度增加而递减,有机质和Org N与TN的垂向分布相似,尽管 NH+4 N的垂直变化分异较大,但仍表现于表层富集的特点。Org N为表层沉积物和沉积柱芯中氮的主导形态,NH+4 N为无机氮的主导形态,成岩过程中,沉积物中TN只有极少部分在发生矿化。沉积物中有机质主要来源于湖中芦苇等大型挺水植物及陆源输入。哈素海表层沉积物的氮污染对底栖生物已经产生了严重的生态毒性效应,对底栖生物群落及整个水生生态系统构成了严重威胁。     

Deformation metamorphism of bituminous and anthracite coals from China

Tectonic displacement of coal seams in China has resulted in faulting parallel to coal bedding. Displacement along these faults caused significant comminution of the coal on the footwall contributing to various mining problems, the worst of which is catastrophic failure, or “outbursting” of the working face during mining. The granular texture and mostly unconsolidated nature of the coal suggests that faulting occurred relatively late in the coalification sequence, at a time of maximum tectonic stress. Coal samples taken on either side of the fault plane (normal and deformed coal layers) were obtained in an effort to establish what influence these tectonic stresses might have had on coal properties as well as what they might reveal about the influence of tectonic pressure on organic maturity. Sample sets were collected within coal beds from undisturbed and adjacent deformed layers, including 21 bituminous samples from the Pingdingshan coal field and nine anthracite samples from the Jiaozuo coal field, the Tieshenggou coal mine of the Yuxi coal field in Henan province, the Beijing Xishan coal field, the Baijiao mine of the Furong coal field in Sichuang province and the Baisha coal field in Hunan province, China. Results from vitrinite reflectance, proximate and ultimate analyses show some differences in reflectance, hydrogen content and nitrogen content of anthracite coal. No significant difference was found between volatile matter yields of normal and deformed coal specimens. GC measurements of the saturated hydrocarbon fraction of chloroform extracts from bituminous coals showed that lower molecular weight carbon fragments were concentrated in the deformed samples. Therefore, although changes in the gross chemical properties of the deformed coal were insignificant, some modification of the chemical structure is seen to have occurred as a result of exposure to tectonic pressure.     

原油族组分在煤中留存能力的研究

研究了煤及其干酪根对不同组分油气的留烃能力.将原油分成5个组分,引入溶胀理论,对低、中、高成熟度的煤及其干酪根在不同溶解度参数的溶剂中进行了溶胀实验,获得不同成熟度的煤及其干酪根的溶胀特征,进而得到不同成熟度的煤及其干酪根对5个组分的留烃能力.R°在0.4%～1.25%范围内的煤及其干酪根,其溶胀比随着煤的成熟度增加而降低;而R°大于1.25%的干酪根,其溶胀度则随着Ⅲ型干酪根的成熟度的增加而升高.在"油窗"范围内,随着成熟度的变化,煤和Ⅲ型干酪根的溶胀比降低,表明其留烃能力在下降.对于具有中等溶解度参数的组分,其留烃能力下降约20%.     

Some chemical structural features of coals of differing maceral distributions and stratigraphy

Six North American bituminous coals (four Carboniferous and two Cretaceous) and eight maceral concentrates from Carboniferous British seams have been heated with tetralin and hydrogen to 400°C. The hexane-soluble parts of the products were separated by column chromatography and the fractions were then analyzed by gas chromatography/mass spectrometry. In all cases the aromatic hydrocarbon fraction was a very complex mixture containing a number of alkylated biphenyls, diphenylmethanes and -ethanes, and polycyclic compounds. However single ioncchromatography (m/z = 142) showed that, in addition to these, the products from five of the six American coals contained homologous series of long chain n-alkylnapththalenes with alkyl groups extending to C₁₆. In other fractions from the American coals, homologous series of n-alkylfurans and alkylphenols were found to be major components, as also were many alkylcyclohexenones related to isophorone. Extensive homologous series of n-alkyl aromatics were not detected in products from any of six vitrinites from British seams, though series of n- and iso-alkylphenols were found in the products from two sporinite concentrates. A number of polycyclic ketones apparently related to sterols were found in the products from the British vitrinites but not from any American coals. Reasons for what appear to be systematic structural differences between the American and British coals are discussed. Differences in stratigraphy are noted and it seems not impossible that differences in source vegetation are significant.     

沱江流域沉积物中氮赋存状态及其垂向分布特征

2004年2月发生在沱江的特大水污染事故给沱江流域的生态环境造成了严重的危害,近年来受工农业和沿岸居民生活的影响,沱江的生态环境依然遭受着一定程度的污染,但对沱江流域氮的地球化学研究甚少。沉积物是水环境中污染元素的重要蓄积库或释放源,为揭示沉积物中氮赋存状态迁移转化特征,并评估该地区生态环境修复状况,本文参照Mackin应用的沉积物中吸附态氨氮提取方法和Smart建立的沉积物中总氮提取方法,采用分光光度法针对沱江流域金堂地区冬季沉积物,开展了河流沉积物中总氮(TN)、可交换态氨氮(AN)、有机氮(ON)赋存状态分析,并对比了十年前后该地沉积物中氮赋存状态的变化情况。实验结果表明:TN含量为518.913~4386.899 mg/kg,ON含量为101.531~3793.683 mg/kg。在-3 cm以上,TN和ON含量较高,且ON是TN的主要组成部分;随着深度增加,两者含量迅速减少,AN含量略有降低。与十年前该地区沉积物中氮的相关数据对比,TN含量增加,其中AN含量增加明显;在-3 cm以上,ON、TN在表层沉积物中增加明显。研究认为:沱江流域沉积物中的氮已经作为内源氮释放至间隙水甚至上覆水中,同时存在外源污染,致使沉积物表层有机氮以及总氮含量升高明显。     

低阶煤显微组分对一氧化碳的吸附性能

研究低阶煤中不同显微组分对CO气体的吸附性能,对低阶煤自燃发火的预测与防治具有指导意义。对低阶煤中的惰质组与镜质组分别进行了30℃、40℃、50℃、55℃、60℃和65℃的等温吸附实验以及煤质分析、煤岩分析和傅立叶红外光谱(FTIR)分析。结果表明:当温度一定(T≤50℃)时,煤对CO的吸附量与压力之间的关系可用Langmuir方程来描述;当温度较高(T>50℃)时,煤对CO的吸附量与压力之间呈线性增加关系,且可采用Henry方程来描述,但此时温度对煤吸附CO的影响较复杂,有待进一步研究;此外,因低阶煤中的丝质体、含氧官能团和负电性官能团含量普遍较高,尤其羟基—OH含量较高,从而对煤中惰质组吸附CO产生较大的影响,而对镜质组吸附CO的影响较小。     

Structure and origin of terpenoid hydrocarbons in some German coals

Hydrocarbon extracts of coal samples from major coal fields in West Germany have been investigated by gas chromatography-mass spectrometry (GC/MS). The samples are of Carboniferous and Tertiary age and derive from limnic and paralic environments, the Saar District, the Ruhr Area and the Lower Rhine Basin.Differences in facies, maturity and age reflected in the distribution patterns of the extracted alkylcyclohexanes. An unexpected occurrence of cyclic diterpenoid hydrocarbons in some samples of Carboniferous age has been found. The tetracyclic compounds mainly show phyllocladane type structures and can serve as source indicators.Hydrocarbons obtained from chemical degradation of the macromolecular material of the samples also revealed phyllocladane-type compounds which are normally associated to resins of modern and extinct familes of conifers. Origin and structural variations of this class of hydrocarbons are discussed in terms of maturity and palaeobotanical implications.     

河流可溶性有机氮研究进展

河流DON不但记录了流域侵蚀的过程,还记录着DON的生物地球化学信息,河流可溶性有机氮其流动是流域生态系统氮循环的重要组成部分。本文综述了河流可溶性有机氮的性质、来源、环境效应、时空变化以及同位素技术应用的最新研究进展,并指出今后河流DON的研究方向。     

龙滩水库枯水期N、P元素空间分布特征

为研究龙滩水库枯水期溶解态氮、磷营养元素的空间分布特征,在龙滩水库枯水期(2017年1月份)进行分层采样,现场测定水体理化性质及实验室分析水中营养盐浓度。结果表明:龙滩水库水温出现明显垂直分层:0~10m为温跃层;10~60m为混合层;60m以下为底温层;pH值为7.63~7.92,水体呈弱碱性。溶解无机氮(DIN)平均浓度为4.75mg/L。水体溶解性氨氮、硝态氮、亚硝态氮平均值为0.07mg/L、2.62mg/L、2.05mg/L,分别占DIN的1.6%、55.2%、43.2%,硝态氮、亚硝态氮是组成龙滩水库溶解无机氮的主要成分。磷酸盐平均浓度为0.04mg/L。参照潜在性富营养化评价标准,N/P(质量比)比值为73.84,说明龙滩水库枯水期属于磷限制潜在性富营养状态,营养状态空间分布特征:坝前水体双江口红水河镇小马场。     

构造煤结构与煤层气赋存研究进展

碎软煤的完整原样制取困难,需要加工制成重塑煤体,为了研究不同压制荷载对煤体物性特征的影响,以重塑煤体为研究对象,基于低温液氮的孔隙测试实验和高压容量法的甲烷吸附实验,探讨不同成型荷载而成的重塑煤体的微小孔结构及其吸附特性的差异。结果表明：不同成型荷载压制而成的重塑煤体,其微孔和小孔的孔容随着成型荷载的增大而略微减少,孔比表面积随着成型荷载的增大而略微增加,总孔体积减少和孔比表面积增加的幅度不大;通过分形理论发现无论高压段还是低压段,孔隙结构具有明显的分形特征,且在高压段的分形维数普遍低于低压段,不同荷载压制而成的重塑煤体的分形维数差别不大;等温吸附线均符合第Ⅰ类等温吸附曲线,Langmuir模型适用于描述重塑煤体的等温吸附,成型荷载对煤的吸附常数有一定的影响,其对吸附常数b值的影响大于对a值的影响。研究不同成型荷载下重塑煤体的吸附特性,为不同条件下型煤制作及冷冻取心实验提供参考。