DIMETHYL SULPHOXIDE-A SOLVENT FOR THE STUDY OF COALS

ABSTRACT

Dimethyl sulphoxide (DMSO) has been found to be a very good solvent for the study of Tow rank coals. Chemical studies of a Texas lignite, its DMSO soluble fraction obtained under ambient conditions, the DMSO insoluble residue and its humic acids have been carried out. Physico-chemical techniques such as Fourier transform infrared spectrometry (FTIR), and ¹³C cross-polarization/magic angle spin (¹³C CP/MAS) NMR spectrometry and chemical methods such as pertri fluoroacetic acid oxidation and the determination of acidic group concentrations have shown that the DMSO-soluble portion possesses a chemical structure which is similar to both that of the neat lignite and of the DMSO-insoluble residue. The humic acids are highly aromatic and acidic in nature. Preliminary data obtained through the use of ²⁵²Cf plasma desorption mass spectrometry (²⁵²Cf PDMS) suggests the existence of a common species in both the DMSO extract and the humic acids.     

STRUCTURE AND REACTIONS OF BEYPAZARJ LIGNITE I. CHARACTERIZATION BY 13C NMR AND IR STUDIES

The solid state ¹³C NMR and infrared spectra of Beypazan lignite were deconvoluied by the least squares curve fitting techniques to resolve the overlapping bands in the 0-220 ppm region of the ¹³C NMR spectra and in the 4000-2700 cm^-1, 1860-900 cm^-1 and 900-400 cm^-1 regions of the infrared spectra to gain information about the structure of the lignite. Measurement of integral absorptivities of some of the functional groups present in the infrared spectra was attempted. Measured values of integral absorptivities are in good agreement with those reported previously.     

13NMR CHARACTERIZATION OF HUMIC MATTER PRESENT IN DIFFERENT OIL SANDS

Insoluble organic matter (humic matter) present in oil sands can alter the wettability of the inorganic matrix and thereby cause serious problems during bitumen recovery.

Using a cold water agitation test, solids rich in organic matter were isolated from various oil sands which were chosen to reflect different behavior in the hot water extraction process.¹³C NMR examination of these separated solids showed significant structural variations between samples isolated from different oil sands. Humic matter from Utah oil sand appeared to be more aliphatic than that derived from Athabasca oil sand.

Humic acids extracted from organic rich solids as a result of prolonged treatment with 2% NaOH show remarkable similarity in their ¹³C NMR spectra. Humins differ substantially in the relative contribution of the terrestrial and marine source material. There was apparent correspondence between poor bitumen separation and the presence of humin with highly paraffinic structures.     

川东北元坝与河坝地区陆相储层天然气成因

在川东北地区石油地质背景特征的基础上,探讨了元坝与河坝地区陆相储层天然气的成因。元坝地区侏罗系储层天然气重烃气体含量较高;多数样品甲烷δ¹³C和δD值分别在-42.2‰ ~-34.4‰ 和-208‰ ~-168‰ ,乙烷δ¹³C值在-31.4‰ ~-21.4‰ ,甲烷δ¹³C和δD值之间相关性好;天然气主要来源于侏罗系自流井组或千佛崖组陆相烃源岩。元坝地区须家河组储层天然气重烃气体含量低;甲烷δ¹³C和δD值分别为-31.7‰ ~-29.2‰ 和-170‰ ~-148‰ ,乙烷δ¹³C值在-27.7‰ ~-26.5‰ ;天然气主要来源于元坝地区上三叠统须家河组高—过成熟的腐殖型烃源岩。元坝地区陆相储层天然气成因的主控因素是陆相烃源岩发育及其成熟度。河坝地区陆相储层天然气重烃气体含量变化大;甲烷δ¹³C值大多重于-32‰ ,甲烷δD值分布范围较大,在-186‰ ~-122‰ ,乙烷δ¹³C值在-33.2‰ ~-29.6‰ ;甲烷δD与δ¹³C值之间相关性很差,部分样品甲烷与乙烷的δ¹³C值倒转,表明河坝地区陆相储层天然气成因复杂,有来源于陆相须家河组的天然气,也有来源于海相烃源岩的天然气,以及海相与陆相来源天然气的混合气。河坝地区陆相储层天然气成因的主控因素是海相与陆相多套烃源岩与不同级别断裂。陆相储层天然气中CO₂的δ¹³C值多轻于-12‰ ,属于有机质热分解成因。稀有气体³He/⁴He比值在0.003 3R_a~0.018 1R_a,分布于地壳来源或放射性成因的范围内,表明天然气中没有幔源稀有气体的贡献。     

CHARACTERISATION OF CYCLIC AND ACYCLIC ALKANES CHARACTERISATION OF CYCLIC AND ACYCLIC ALKANES IN FORTIES AND KUWAIT PETROLEUM CRUDES

Alkane hydrocarbon fractions from Forties (North Sea) and Kuwait petroleum crudes, separated by distillation, solvent extraction and silica-gel column chromatography and sub-fractionated by molecular-sieve adsorption, have been examined by gas chromatography (GC) ¹H and ¹³C ( NMR spectroscopy, GC-mass spectrometry (MS) and field desorption (FD)MS. GC indicates that Forties contains rather more acyclic isoprenoids and cyclic alkanes than Kuwait; FDMS of Kuwait shows molecular-weight ranges for mono-, di-, tri-, tetra- and pentacyclic alkanes. ¹³C NMR spectra provide evidence of higher aromatic carbon, C_A, in Forties than Kuwait and longer T₁ relaxation times.     

STUDY OF STRUCTURAL FEATURE OF PEAT, LIGNITE AND HUMIC ACID BY SOLID STATEl3C NMR SPECTROSCOPY

Four low rank coals (peat and lignite) and their derived humic acids have been investigated by the^l3C CP/MAS/TOSS NMR technique. The NMR analysis indicates that the peat contains a significant amount of unaltered plant components including cellulose, hemicellulose, lignin, waxes, and resins.

Variable contact time and dipolar dephasing experiments were performed on each sample. The data from above experiments, together with normal CP/MAS integration over selected chemical shift range, were used to derive 12 parameters of carbon skeletal structure including the aromaticity.From the ratio of aromatic bridgehead carbons, f_a^cp, to the aromatic peripheral carbons, f^cpxBp as measured by NMR, the aromatic cluster size may be estimated for each coal.     

挥发作用对C5—C8轻烃指标的影响：模拟实验证据

C₅—C₈轻烃指标在石油勘探开发中扮演着重要角色,然而其易挥发的自然属性导致C₅—C₈轻烃指标在实际应用过程中存在诸多不确定性。本研究利用塔中地区奥陶系海相凝析油在实验室内进行了原油挥发模拟实验,基于实验结果遴选和构建了受挥发作用影响较小的系列轻烃指标,具有较强的实用性。模拟实验结果显示挥发作用对C₅—C₈轻烃指标的影响程度受轻烃分子量和分子构型共同控制。nC₅—nC₈正构烷烃挥发量随正构烷烃碳数增加而逐步降低,不同分子构型C₇化合物挥发量由高到低依次为：C₇-支链烷烃>nC₇>甲基环己烷>甲苯,二甲基环戊烷挥发量则大体相当。正（异）构烷烃与环烷烃比值和挥发速率相近的相同分子构型轻烃比值受挥发作用影响相对较小。原油挥发过程中,残留液态原油内C₆—C₈轻烃单体稳定碳同位素组成随挥发量增加逐步富集¹³C,nC₆—nC₈正构烷烃稳定碳同位素组成变化程度随碳数增加逐渐降低。当C₆—C₈轻烃挥发量小于70% 时,C₆—C₈轻烃稳定碳同位素组成变化不大,当其挥发量大于70% 时,正构烷烃、异构烷烃和芳烃稳定碳同位素组成均产生1.0‰ 以上的较大变动,环烷烃稳定碳同位素组成则变化不大。受挥发作用影响较小的轻烃指标即正（异）构烷烃与环烷烃比值和环烷烃稳定碳同位素组成在塔中地区原油成熟度标定和原油类型划分方面取得了较为理想的应用效果,展现了良好的实用性和应用前景。     

SPECTROSCOPIC STUDIES OF PETROLEUM RESINS

Resin fractions containing heteroatoms obtained from deasphaltened oils of petroleum residues (500^°C+) of Bombay High 7lpar;BH) and Gujrat Crude Mix (GCM) have been separated into acidic, basic and neutral Lewis base (NLB) types employing chromatographic methods. Ultimate compositions of these fractions have been determined for deducing the average molecular formulae. Infrared spectroscopy has been employed for assigning various heteroatomic functional groups and estimating compound types. The distribution of various types of carbon (relative as well as atomic) and hydrogen has been computed from ¹³C- and ¹H-NMR spectra of these subfractions.     

中国含油气盆地有机烷烃气碳同位素特征

本文根据中国16个含油气盆地815个气样δ¹³C_1-4的1851个分析数据,探讨了中国有机烷烃气碳同位素特征,认为有机烷烃气的δ¹³C值随成熟度(R₀)增大而增加;有机的同源同期的甲烷及其同系物的δ¹³C值随烷烃气分子中碳数增加而增大;相同或相近成熟度源岩形成的煤成气的甲烷及其同系物的δ¹³C值比油型气的对应组份的δ¹³C值重;甲烷及其同系物中某个或某些组份被细菌氧化后可使其剩余组份的碳同位素变重.     

HYDROLIQUEFACTION OF TEXAS LIGNITE IN COAL- AND PETROLEUM-DERIVED SLURRY OILS

Hydroliquefaction of Texas lignite (68.5%. C daf) was conducted in a batch autoclave under hydrogen in a coal-derived slurry oil at 90 bar initial pressure for temperatures of 380-460^° C and residence time of 15-60 minutes, or a vacuum distillate from petroleum at 435^° C for 60 minutes and initial H₂-pressure of 60-150 bar, or a vacuum residue from the same petroleum at 435 and 460^° C for 60 minutes and initial H₂-pressure of 90-150 bar or tetralin at 435^°C, 60 minutes and 90 bar initial H₂-pressure. Red mud plus sodium sulfide were added as a catalyst for all experiments. Lignite conversion ranged from 50 to 83%. The products were separated into gases, residue, asphaltenes, oils B,P. above 200^° C, oils B.P. below 200^° C. Total liquid products from coal reached 57% in coal-derived slurry-oil, 56% in vacuum distillate and 64% in vacuum residue at optimum conditions with 32% of product oil B.P. below 200^° C in vacuum distillate and 24% in vacuum residue. When coprocessing lignite with vacuum residue at 120 bar initial pressure, 435^°C and 60 minutes residence time the total mass balance presented an oil yield of 73%. with 32% boiling below 200^°C.     

A Study on NMR and GC/MS Spectra of the Isomers of Linear Hexyl Naphthalene

The GC/MS and NMR analysis of the reaction products of naphthalene with 1-bromohexane were reported. The products obtained were suggested to have six isomers of linear hexylnaphthalene and the structure of each isomer was determined by GC/MS and NMR spectra. For the first time, the unique chemical shift data were obtained. The content of each isomer calculated by ¹H NMR and ¹³C NMR spectra was consistent with that by GC/MS spectra, which confirmed the accuracy of NMR data.     

13C SOLID STATE NMR OF ALBERTA SUBBITUMINOUS MACERALS

The relaxation time behavior for three macerals (vitrinite, fusinite, and resinite) of a subbituminous coal has been extensively characterized by ¹³C solid state nor. Parameters studied included free radical concentrations. ¹³C spin-lattice relaxation, T₁^C, cross polar1zation times, T_CH, proton rotating frame spin-lattice relaxation. T_1P^H. dipolar dephasing times. T₂¹, aromaticity, f_a, and the effects of spinning sideband suppression on f_a,. Large chemical shift variations among these samples were observed and assigned to various possible structural entities. Correlations between proximate and ultimate analyses and the nmr results, as well as comparisons with previously reported relaxation times are made.     

准噶尔盆地南缘油气生成与分布规律——原油地球化学特征与分类

准噶尔盆地南缘地区原油分布广泛,不同地区原油具有不同的地球化学特征。按照碳同位素与生物标志物组成特征可以分为4种典型类型:1第1类原油典型特征是碳同位素组成轻,全油δ¹³C值通常小于-29‰,正构烷烃分子碳同位素分布比较平缓,δ¹³C值通常小于-28‰,含有较丰富的β-胡萝卜烷,甾烷以C₂₈、C₂₉规则甾烷为主,重排甾烷低,伽马蜡烷含量变化较大;2第2类原油碳同位素组成重,全油δ¹³C值通常在-28‰~-26‰,正构烷烃分子碳同位素分布比较平缓,δ¹³C值通常大于-28‰,Pr/Ph比值高,甾烷以C₂₉规则甾烷和重排甾烷为主,三环萜烷以C₁₉为主,伽马蜡烷含量很低;3第3类原油碳同位素组成轻,全油δ¹³C值通常小于-29‰,C₉以上正构烷烃分子碳同位素分布随碳数增高大幅下降,δ¹³C值在-27‰~-34‰,Pr/Ph比值小于1.0,C₂₇、C₂₈、C₂₉甾烷呈"V"型分布,异胆甾烷、重排甾烷含量高,Ts、C₂₉Ts、C₃₀重排藿烷高,Ts/Tm >1,伽马蜡烷含量高且具有两个异构体,甾/萜烷比值高;4第4类原油碳同位素组成重,全油δ¹³C值通常在-28‰~-26‰,C₉以上正构烷烃分子碳同位素分布随碳数增高下降幅度大,δ¹³C值在-23‰~-29‰,C₂₇、C₂₈、C₂₉甾烷呈"V"型分布且以ααα-20R为主,异胆甾烷丰度低,甲藻甾烷尤为丰富,三环萜烷以C₁₉为主,伽马蜡烷含量较低。     

STRUCTURAL CHARACTERIZATION OF PETROLEUM BASED FEEDSTOCKS FOR CARBON BLACK PRODUCTION

Some selected petroleum based feedstocks have been characterized by ¹H and ¹³C NMR spectroscopy for their possible use as carbon black feedstock (CBFS). Feedstocks studied are pyrolysis tars, clarified oils, aromatic extracts and vacuum residue. Analysis of average structural NMR parameters show that pyrolysis tars because of their being highly aromatic in character (high BMCI) are the most suitable feedstock for carbon black. Aromatic extracts rank the next. Clarified oils of Indian refinery origin needs further processing due to middle distillate mode refining severity.     

CHARACTERIZATION OF HEAVY OIL FRACTIONS OBTAINED FROM THERMAL TREATMENT IN PRESENCE OF SULFIDES AND H-DONOR ADDITIVES

Analytical studies have been performed on effluents issued from thermal conversion of Safaniya Vacuum residue (Arab Heavy) in presence of tetralin, thiophenol and methyldisulfide. In contrast to thermal behavior of the heavy oil alone, low coke amount was produced at high conversion level (up to 50%) beside good product qualities as demonstrated from analysis of the remained 500°C⁺ fractions. H-donor diluent and sulfide additives help effectively in lowering the carbon residue values and maintaining the H/C ratios at the highest values compatible with the conversion. Microstructural parameters of the liquid effluents and their asphaltenic parts are obtained ¹H and ¹³C NMR spectroscopy and average molecular weight determination. Even at high conversion level results allow to assess a rapid dealkylation process at the first stage of the thermal treatments associated with a good control in the evolution of the size of polyaromatic units. Optical Microscopy and X-ray analysis outline the specific effect of tetralin as a. delayed coking additive.     

STRUCTURAL STUDIES OF SHORT PATH DISTILLATES AND SUPERCRITICAL FLUID EXTRACT OF PETROLEUM SHORT RESIDUE BY NMR SPECTROSCOPY

Four short-path distillates obtained at different evaporator temperatures (240, 270, 300, and 330° C) and a supercritical fluid extract (with CO₂ as solvent) of petroleum short residue (North Gujarat Mix) have been separated into saturates and aromatics. Each fraction of all the said samples has been studied by ¹H- and ¹³C-NMR spectrometry and the distributions of various types of hydrogens and carbons are reported. Several reliable average structural parameters have been computed and their relative variation is discussed.     

鄂尔多斯盆地奥陶系碳酸盐岩成岩相碳、氧稳定同位素特征

根据岩石薄片及阴极发光图像,研究了鄂尔多斯盆地奥陶系碳酸盐岩成岩相类型及岩相特征。据碳、氧稳定同位素(δ¹³C, δ¹⁸O)分析数据,研究了各类成岩相的地球化学特征。奥陶系海相碳酸盐岩台地在早古生代处于近地表成岩域,划分为正常海水、蒸发海水、早期大气淡水及热海水4类成岩环境及成岩相。正常海水、热海水及蒸发海水成岩相的δ¹⁸O和δ¹³C值普遍较高,随生物碎屑含量增加δ¹⁸O及δ¹³C值趋于减小;早期淡水成岩相的δ¹⁸O和δ¹³C值普遍较低。晚古生代,奥陶系顶部进入表生期成岩域,据目前残存地层的岩石类型,表生期成岩域可划分为峰峰组的灰岩风化成岩相和马家沟组的云岩风化成岩相,其δ¹⁸O和δ¹³C值明显低于早期淡水成岩相的值。晚古生代末期,奥陶系进入3 000~4 000 m的中-深埋藏成岩域,划分为封闭系统及开放系统成岩相。封闭系统成岩相的δ¹⁸O和δ¹³C值主要继承了其原岩的δ¹⁸O和δ¹³C值特征;而在开放系统中,由于同位素高温分馏作用,其成岩相的δ¹⁸O和δ¹³C值则大幅度降低。研究结果表明,碳酸盐岩岩相特征及碳、氧稳定同位素组成是追溯碳酸盐岩成岩环境及识别和划分成岩相的重要指标。     

Synthesis and Characterization of Mono-Isomeric Alkylbenzene Sulfonates

The synthesis of a series of isomer pure mid-position alkylbenzene sulfonates is described. Three isomers—4-(1-ethyldodecyl)benzene sodium sulfonate, 4-(1-butyldecyl)benzene sodium sulfonate, and 4-(1-hexyloctyl)benzene sodium sulfonate—were synthesized. High performance liquid chromatography (HPLC) indicated that the isomers were of 99.9%, 96.2%, and 97.5% purity, respectively. Their structures were characterized to be correct by electrospray ionization-mass spectrometry (ESI-MS), ¹H NMR, and ¹³C NMR investigations. Furthermore, the purity and structure of the three kinds of intermediates were also determined by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS).     

酒西盆地砂岩储层碳酸盐胶结物分布及碳、氧稳定同位素富集特征

碳酸盐胶结物是酒西盆地石油沟油田古近系白杨河群间泉子组（N₁b₁）M油组砂岩储层中最重要的自生矿物,其含量及分布是储层定量评价的主要参数。通过矿物学、岩石学和地球化学测试分析认为,该区碳酸盐胶结物主要以方解石为主,少量白云石胶结物,胶结物分布范围为2.11%~56.39%,平均为12.93%。碳酸盐胶结物以基底式、孔隙式结构为主,部分斑点状、环边状。研究表明,不同微相砂体中碳酸盐胶结物相对含量明显不同,其中沙坝微相含量最高,平均为14.6%,河心滩微相含量最低,平均为8.09％,而滞留沉积微相含量居中,平均为7.73％。碳、氧稳定同位素分析表明,δ¹⁸O（PDB）值为-11.14‰~-3.25‰,δ¹³C（PDB）值为-7.32‰~-0.42‰,显示了该区碳酸盐胶结物来自淡水—微咸水环境,与溶解—沉积作用相关。δ¹³C、δ¹⁸O 值呈现由深部到浅部逐渐变小、变轻的趋势,说明由深到浅大气淡水影响逐渐增强,水体盐度减小,成岩温度逐渐增高。研究还发现,碳酸盐胶结物δ¹⁸O、δ¹³C值的分异与油气富集程度具较好的分区性,油浸—含油级砂岩碳酸盐胶结物富集δ¹³C,油斑—油迹级砂岩缺少δ¹⁸O同位素,荧光级砂岩胶结物同时缺少δ¹⁸O和δ¹³C同位素。     

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��There are two kinds of coal-formed gas the coalseries gas and the gas in coal bed, and each has its own chemical composition and carbon isotope characteristics of methane.The gas in coal bed is rich in ¹²C, because of the exchange of carbon isotope between the gas in coal bed and the CO₂ or the organism reaction.The coal-series gas is formed from the organic matter dispersed in coal-series and rich in ¹³C.The research of carbon isotope of methane has important significance for the clarification and origin of the coal-formed gas as well as for the resource esti mation.