Structural relationships between a brown coal and its kerogen and humic acid fractions

A South Australian Tertiary brown coal is fractionated into humic acid and kerogen fractions. These related samples are then subjected to a number of different analytical techniques including infrared and¹³C-Nuclear Magnetic Resonance spectroscopies and pertrifluoroacetic acid oxidation. Structural conclusions are drawn from an integrated consideration of the data. Brown coal aliphatic structure is concentrated in the kerogen and the solvent soluble polar acid fractions. The humic acids are the most aromatic and contain a high degree of hydrogen bonding. Only very minor amounts of long polymethylene chain structures are observed in the humic acids, in complete contrast to the kerogen fraction. Different organic detrital origins are proposed for the coal fractions.     

CPMAS 13C NMR spectra of estuarine sedimentary humic acids

CPMAS ¹³C NMR spectra of two estuarine sedimentary humic acids were recorded on a Bruker WP-SY 200 spectrometer. Both samples were found to contain similar aromatic and aliphatic carbon fractions. The sedimentary humic acids have unusually high methoxyl contents and more than one type of methoxyl is indicated. The high methoxyl content may be related to relatively low values for estuarine sedimentary humic acid-metal complexes. Carbohydrate contents of the humic acid samples were also found to be low.     

Aliphatic components of Victorian brown coal lithotypes

Victorian brown coal occurs in five major lithotypes distinguishable by colour index, petrography and bulk chemical analyses. The distributions of solvent extractable (free) and base hydrolysable (bound) n-alkanes, n-monocar?ylic acids, n-?,ω-dicar?ylic acids, n-ω-hydroxycar?ylic acids and n-alcohols were determined for samples of each of the five lithotypes (lithotype profile) and for seven samples of identical lithotype classification spanning a 100 m interval (depth profile) taken from a continuous bore core. The distributions of free molecular components in all classes are indicative of the predominant higher plant origin of this immature coal and provide strong support for the view that different lithotypes have derived from different, yet fairly specific paleobotanical communities. Despite an overall similarity in the distributions of aliphatic components from samples of identical lithotype classification, changes in the absolute concentrations and carbon preference indices (CPIs) of specific functional classes are observed in response to catagenetic influences even across the very small rank interval of the depth profile samples. Molecular distributions of bound components are similar to those of their free counterparts except that CPIs are generally lower and the relative contributions of lower molecular weight homologues (i.e. <C₂₂) are higher. Thedistributions of bound dicar?ylic acids and hydroxycar?ylic acids appear to reflect variations in the oxic/anoxic nature of the depositional paleoenvironments.     

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。     

风化煤及提腐植酸后残渣热解行为与动力学分析

应用热重-质谱(TG-MS)联用技术对风化煤(WC)及其腐植酸提取后残渣(WCR)的热解行为进行了研究,分析了非烃类(H2、H2O、CO和CO2)、低碳烃类(CH4、C3H6和C3H7)和芳烃类(C6H6)的实验结果,并利用Coast-Redfern积分法对其热解和烃类生成动力学进行了探讨,获得了热解过程和烃类生成动力学参数。结果表明:热解过程中风化煤的质量损失率(38.9%)略大于其腐植酸提取后残渣(36.6%);除CO和CO2外,残渣中非烃类、低碳烃类和芳烃类产物的逸出量都稍微或显著多于风化煤中各类组分的逸出量。用Coast-Redfern积分法求得的动力学参数很好地解释了这一结果。     

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。     

Molecular weight distribution,analytical and spectroscopic characterization of humic fractions sequentially isolated by organic solvents from a brown coal humic acid

A sequential fractionation procedure employing a series of selected mild organic solvents of different polarity has been applied for the isolation of chemically different organic fractions from a brown coal humic acid. Elemental composition, molecular weight distribution, i.r. and electron spin resonance analysis were carried out on the isolated humic fractions. They were characterized by: (a) a low polydispersity, (b) a decreasing aliphatic and increasing aromatic character along the series, (c) very different molecular weight which significantly correlated with E₄/E₆ ratios (particle aggregation and molecular association) and free radical concentrations (chemical and biochemical activity). Significant correlations were found between physico-chemical parameters of the isolated humic fractions, i.e. M_n, M_w, E₄/E₆ ratios, spins/g contents and the dielectric constants of the solvents used. This suggested the efficiency of the applied procedure in isolating chemically different organic fractions from the bulk, original humic acid.     

弱氧化气氛下烟煤热解特性及热解产物组成

为提高轻质焦油和煤气产率,选取陕西红柳林烟煤为研究对象,采用固定床反应器对比分析N₂气氛和弱氧气氛下（N₂+O₂）煤的热解产物产率分布及组成特性。结果表明：随着O₂的加入,半焦和焦油产率显著降低,CO和CO₂气体产率显著增大,导致总气体产率增大;由于发生氧化燃烧反应,随着热解气氛中氧含量的增大,H₂、CH₄和C₂—C₃产率逐渐降低,在此过程中水产率变化幅度较小;弱氧气氛下焦油分解温度大于N₂气氛,酚类物、脂肪烃及苯系物在弱氧气氛下热解焦油中的相对含量较低,且多环芳烃相对含量明显大于N₂气氛下热解焦油。当热解温度为800℃,过量空气系数ER=0.14时,焦油产率为6.22%,H₂产率14.01 mg/L,焦油和H₂产率达到最佳值。由于弱氧气氛下热解得到半焦的石墨化程度低于N₂气氛下的热解半焦,导致弱氧气氛下半焦反应活性大于N₂气氛。研究结果为固定床热解烟煤制备高值燃料提供基础数据。     

黄县盆地褐煤与油页岩的泥炭沼泽类型分析

对黄县第三纪褐煤与油页岩共生盆地中煤₁和油₁的煤岩学特征及煤相参数特征的分析表明,黄县盆地煤₁形成于较深覆水的森林沼泽,油₁形成于湖泊沼泽,而海水侵入控制着盆地的覆水变化,进而影响了植物群落的演化与更叠。     

Effect of humic acids on numbers and activities of micro-organisms within physiological groups

The incorporation of humic acid fractions in media designed for the enumeration of soil micro-organisms belonging to specific physiological groups was found to result for some groups in appreciably higher counts. It is suggested that by influencing the enzyme systems of certain micro-organisms, humic compounds may affect the range of substrates which they can utilize. The effect could have implications on the activity of organisms in environments in which humic substances are normally present, such as soils and natural waters.     

Chemical coagulation of humic substances: A comparison of natural aquatic versus soil-extracted materials

Aquatic humic substances can be removed by chemical coagulation during water treatment. Hydrolyzing metals such as Al(III) and Fe(III), as well as commercially available cationic polyelectrolytes, can effectively remove humic substances prior to chlorination, thus reducing the formation of trihalomethanes. Synthetic waters, produced by adding soil-extracted fulvic acids to distilled water containing a clay source and various salts, have some merit in approximating the behavior of aquatic humic substances during chemical coagulation; however, caution must be exercised in the interpretation and applicability of the results.     

黄县盆地褐煤与油页央的泥炭沼泽类型分析

对黄县第三纪褐煤与油页岩共生盆地中煤1和油1的煤岩学特征及煤相参数特征的分析表明，黄县盆地煤1形成于较深覆水的森林沼泽，油1形成于湖泊沼泽，而海水侵入控制着盆地的覆水变化，进而影响了植物群落的演化与更叠。     

Palynostratigraphy of the Erkovtsy field of brown coal (the Zeya-Bureya sedimentary basin)

The Erkovtsy brown coal field in the northwestern Zeya-Bureya sedimentary basin (129°–130° E, 46°–47° N) is structurally confined to southern flank of the Mesozoic-Cenozoic Belogor’e depression. The verified stratigraphic scheme of the coalfield sedimentary sequence is substantiated by palynological data on core samples from 18 boreholes sampled in the course of detailed prospecting and by paleobotanical analysis of sections in the Yuzhnyi sector of the coalfield (data of 1998 by M.A. Akhmetiev and S.P. Manchester). Sections of the Erkovtsy, Arkhara-Boguchan, and Raichikha brown-coal mines are correlated. Stratigraphic subdivisions distinguished in the studied sedimentary succession are the middle and upper Tsagayan subformations (the latter incorporating the Kivda Beds), Raichikha, Mukhino, Buzuli, and Sazanka formations.     

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。     

Oxygen-containing functional groups in land-derived humic acids—II. Changes in the oxygen distribution of humic acids during early diagenesis as revealed by derivatization methods

Extensive functional group analyses were performed on humic acids representative of eight increasing depth levels from a core drilled in the Mahakam delta (East Kalimantan, Indonesia). Oxygen amounts decrease observed during early diagenesis was related chiefly to loss of hydroxyl (lignol?) groups. Comparison between upper and deeper levels shows the following variations: hydroxyl group abundances go from 19 to 6% of humic oxygen. Identified functional groups amounts represent 47 to 32% of weight of moisture- and ash-free humic acids. No evidence of decarboxylation of humic material was detected.     

中国西北侏罗纪煤系显微组分生烃潜力、产物地球化学特征及其意义

从吐哈盆地侏罗纪煤中分离富集了藻类体、孢子体、角质体、镜质体、基质镜质体和丝质体6种主要显微组分,进行了热解及热模拟实验,并对各显微组分热模拟生成的产物热解油进行了碳同位素组成等分析。各显微组分热解生烃潜力及其热解产物热解油的碳同位素组成表明,煤系有机质中藻类体的生油潜力最高,生成的液态烃类的碳同位素组成最轻;孢子体、角质体等陆源富氢组分生烃潜力低于藻类体,生成的液态烃类的碳同位素组成重于藻类体生成的液态烃类,与煤系含油气盆地中原油的碳同位素组成基本一致。这些富氢显微组分应该是煤系有机质中主要的生油显微组分。镜质体和基质镜质体的生油潜力相对较低,其生成的液态烃类的碳同位素组成比一般煤系原油重得多,而且这些组分本身对液态烃具有较强的吸附力,尽管其在煤系有机质中所占的比例很大,仍然难以成为生成液态石油的主要显微组分,只能在高成熟演化阶段成为良好的生气显微组分。丝质体等惰性组分生烃潜力极低,不可能成为生油组分。此外,结合原煤的显微组分组成、生烃潜力和元素分析,提出仅仅以壳质组的含量高低来评价煤的生烃潜力不完全可靠,热解是经济、快速、有效的评价方法。     

On the metal content and metal ion uptake of botanically specific peats and the derived humic acids

With respect to ten metals (Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga) which are continguous in the Periodic Table the natural metal content and the ability to take up metal ions has been determined for three peats of defined botanical origin, each peat being sampled at three different levels. A correlation is found between the natural metal content and botanical origin. Apart from aluminium, the concentration of individual metals increased in the series Sphagnum < fen sedge < reed, the increase being statistically significant (P = 0.001) for V, Mn, Co, Ni, and Ga and for the sum of the metal ions measured.No clear correlation emerged between botanical origin and metal uptake. The metal uptake by the humic acid derived from each peat sample was also determined, and correlated with the metal uptake of the source peat itself.In all the humic acid and peat metal-uptake experiments the selectivities were very similar. V, Cr, Cu, Ga were readily taken up while Mn, Co and Zn were consistently less preferred.     

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.     

Use of ultrasonic treatment for extraction of humic acid with inorganic reagents from soil

The use of ultrasonic vibrations (1 hr) on the extraction of humic acids (HA) from a brown soil has been compared with the extraction by mechanical stirring (24 hr) with two extractants: 0.5 N and 0.1 M Na₄P₂O₇, followed by extraction with 0.5 N NaOH. In the pyrophosphate extraction, ultrasonic and mechanical treatments produced the same yield of HA. Further extraction with NaOH and mechanical stirring gave higher yields.The elemental composition of HA changed remarkably with both ultrasonic and mechanical systems. The HA extracted with ultrasonic treatment showed a higher ash content and a lower content of COOH and phenolic OH groups. These HA's showed higher optical density at 260 and 450 nm when pyrophosphate-extracted, and lower optical density when NaOH-extracted. Moreover the ultrasonic-treated HA in both extractants showed a lower E₄₀₀/E₆₀₀ ratio.Infrared examination confirmed the difference in chemical characteristics of extracted HA. The HA distribution in the different classes of nominal molecular weights by Sephadex gel filtration was influenced by both ultrasonic and mechanical systems, specially for molecular weights between 5000 and 150,000. It has been noted that the differences due to both systems are less marked than those caused by ssing different extractants.     

Pyrolysis-GC-MS and NMR studies of dissolved seawater humic substances and isolates of a marine diatom

¹³C- and ¹H-NMR spectra were obtained for humic substances isolated from a coastal marine environment and also for the intracellular and extracellular extracts of a marine diatom. Phaeodactylum tricornutum Bohlin. Highly branched alkyl chains constitute a large proportion of the structure of the marine humic material, whereas aromatic components are less important. Carbohydrate-type materials, possibly uronic acids, are also present in appreciable amounts. Furans (derived from carbohydrates). pyrroles and nitriles (derived from proteins, nucleic acids and/or tetrapyrroles) and phenols and methylphenols (non-lignin derived) are pyrolysis products derived from pyrolysis-gas chromatography-mass spectrometry of the extracts. The results indicate the similarities in chemical structure of P. tricornutum exudate and dissolved marine humic material.