Hydrous pyrolysis of a Type III source: fractionation effects during primary migration in natural and artificially matured samples

A core from the Cambay Shale Formation of the Cambay Basin, containing immature Type III organic matter, was pyrolysed at 300°C for different durations of time to different maturation levels. Fractionation effects were studied employing a three-step extraction technique after removal of the expelled pyrolysate. The extractable organic matter (EOM) obtained on extraction of the whole core is assumed to be that present in open pores, while that obtained on finely crushing the sample is assumed to be that present in closed pores. The EOM obtained from 1 cm chips is termed EOM from semi-open pores. The gross composition of the pyrolysates expelled during pyrolysis is not similar to the oils reservoired in the area, and there is no significant fractionation observed between expelled pyrolysates and unexpelled EOM. Our study indicates movement of fluids between closed, semi-open and open pores. In both systems, there is a higher concentration of EOM in open pores than in semi-open and closed pores, and the fraction of EOM in open pores is much greater in the artificial system than in the natural system. Fractionation effects on n-alkane and isoprenoid hydrocarbon-based parameters were also studied. n-Alkenes are present in semi-open and closed pores of the immature core and in the core after it was pyrolysed to 300°C for 6 and 48 h, but are absent in the open pores. n-Alkenes are present in closed pores in the naturally matured core. Presence of n-alkenes in the pyrolysates expelled during the 6 and 48 h experiments, but their absence in the open pores of the core, indicates that expulsion also occurs through temporary microfractures during laboratory pyrolysis, whereas in the natural system expulsion from closed pores seems to be only via semi-open and open pores.     

煤系热解参数及其与有机碳的相关性

通过对煤系热解参数之间及其与有机碳含量的研究,分析了煤系热解参数与有机碳的关系,认为煤系热解参数及有机碳含量变化范围均较宽,不同热解参数之间具有一定的相关性。Ｓ１、Ｓ２和Ｓ１＋Ｓ２与有机碳具正相关关系,基本可以用于评价有机质丰度。热解类型指数Ｓ２／Ｓ３、氢指数、氧指数和Ｓ３明显地受有机碳的影响,尤其Ｓ２／Ｓ３受到的影响更为明显,这样就影响有机质类型的评价。给出了各参数间的相关关系式,这对于煤系烃源     

鄂尔多斯盆地北部盒8段古含气范围的地球化学特征

鄂尔多斯盆地盒8段气藏为深盆气藏。通过分析鄂尔多斯盆地苏里格庙地区盒8段储集层中有机包裹体的丰度、储集层的热解特征,并结合该区的构造演化和生烃演化等特征,探讨了苏里格庙北部盒8段气层的古含气边界的变化情况及天然气的保存条件。认为盒8段气层的分布范围在早白垩世末期达到最大,后期的构造抬升对气水边界的影响并不大,这是因为构造抬升后,气源岩的压力下降,增加了煤系地层中吸附气的脱附能力,为气藏补充足够的气体,从而使得古气水边界的分布与现今的差别不大。地层倾角的大小能影响天然气的富集和保存,地层倾角相对平缓的斜坡部位利于天然气的聚集,是高产气区。     

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。     

Primary cracking of kerogens. Experimenting and modelling C1, C2–C5, C6–C15 and C15+ classes of hydrocarbons formed

Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C₁, C₂–C₅, C₆–C₁₅ and C₁₅₊). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.     

A combined pyrolysis mass spectrometric and light microscopic study of peatified Calluna wood isolated from raised bog peat deposits

Stem wood of the Angiosperm Calluna vulgaris (Scotch heather), isolated at different depths from a selection of raised bog peat deposits, was chemically characterized using in-source pyrolysis mass spectrometry (Py-MS) and Curie-point pyrolysis gas chromatography mass spectrometry (Py-GC-MS). Light microscopy was performed to relate mass spectrometric characteristics with anatomical features. Peatified wood samples, isolated from increasing depth show a gradual decrease in carbohydrate content. This decrease in anatomically reflected in a selective removal of secondary cell wall material from the fibre-tracheids and wood parenchyma. During prolonged peatification a selective removal of hemicellulose sugars is observed, while a part of the cellulose fraction is preserved. This highly resistant cellulose is mainly located in the secondary cell walls of the vessels. The lignin macromolecule is preserved, but a gradual decrease in syringyl to guaiacyl ratio (S/G) is observed during peatification. Because no increase in catechol and phenolic compounds is observed, we conclude that S/G shifts are due to removal the of syringyl-rich secondary cell wall material and the retention of guaiacyl-rich compound middle lamella. Small chemical changes in the lignin macromolecule involve shifts in oxygen substitutions on the aliphatic side chains of the methoxyphenolics and the occurrence of aromatic acids.     

Biomarker distributions in asphaltenes and kerogens analysed by flash pyrolysis-gas chromatography-mass spectrometry

Biomarker distributions in a suite of asphaltenes and kerogens have been analysed by flash pyrolysis directly coupled to a GCMS system. Attention has been focussed on biomarkers of the sterane and triterpane types. The sample suite under investigation consists of sediments with different kerogen types and some crude oils. Biomarker distributions in the pyrolysates have been compared with the “free” biomarkers in the corresponding saturated hydrocarbon fractions.The analyses show significant differences between the distributions of the free biomarkers and those in the pyrolysates. The latter have lower amounts of steranes while diasteranes are absent or present at low concentrations only. In the triterpane traces a shift of maximum intensity from C₃₀ (free compounds) to C₂₇/C₂₉ is observed. Furthermore, the pyrolysates contain a set of triterpenes (not present among the free compounds), and there is a selective loss of “non-regular” triterpanes that are present in the saturated hydrocarbon fractions. The observed differences between pyrolysates and free hydrocarbons can be explained partly by the processes occurring during pyrolysis such as bond rupture and subsequent stabilisation of primary pyrolysis products. To a certain extent these differences also show that maturation processes occurring in sediments have effects on free biomarker molecules different from those on molecules that are enclosed in a macromolecular matrix (kerogen or asphaltenes).Differences between biomarker distributions of asphaltene and kerogen pyrolysates are relatively small. A comparison with the pyrolysates from extracted whole sediments suggests that these differences are mainly caused by interactions between the organic material and the mineral matrix during pyrolysis.Oil asphaltenes behave differently from sediment asphaltenes as their pyrolysates are more similar to the corresponding saturated hydrocarbon fractions, i.e. the differences described above are observed to a much smaller extent. This different behaviour appears to be the result of coprecipitation of a part of the maltene fraction with the oil asphaltenes.     

现代松粉热模拟产物的碳氢同位素特征及其地质意义

对现代松粉的在热模拟过程中生成的甲烷,乙烷,丙烷及干酪根碳同位素分析表明,低温阶段（２５０℃以下）松粉热模拟生成的甲烷相对较高温阶段生成的甲烷更富集＾１３Ｃ,松粉热模拟残余干酪根松粉原样稍微富集＾１２Ｃ,反映低温阶段的热模拟产物主要来源于相对富集＾１３Ｃ的松粉原生质,高温阶段（３００℃以上）松粉热模拟生成的甲烷,乙烷,丙烷的δ＾１３Ｃ值随温度升高而富集＾１３Ｃ,松粉热模拟残余干酪根的碳同位素组成没     

Laboratory sulfurisation of the marine microalga Nannochloropsis salina

To understand more fully the mode of preservation of organic matter in marine sediments, laboratory sulfurisation of intact cells of the cultured microalga Nannochloropsis salina was performed using inorganic polysulfides in seawater at 50°C. Solvent extractable and non-extractable materials were analysed by GC–MS and Py–GC–MS, respectively, to study the incorporation of sulfur into the microalgal organic matter. No GC-amenable sulfur-containing compounds were found in the extracts apart from some minor thiophenes with a phytanyl carbon skeleton. The residue after extraction and hydrolysis contained abundant macromolecular sulfur-containing moieties as revealed by the presence of dominant C₂₈–C₃₂ thiols, thiophenes, thianes and thiolanes in the flash pyrolysates. These products are thought to be formed from moieties derived from sulfurisation of C₂₈–C₃₂ diols and alkenols, characteristic lipids of N. salina. C₁–C₂ alkylated thiophenes were also found in the pyrolysates and probably result from moieties formed upon sulfurisation of carbohydrates. The highly resistant biomacromolecule (algaenan) synthesised by N. salina remains unaffected by sulfurisation. The non-hydrolysable residue isolated from the sulfurised N. salina thus comprises algaenan and (poly)sulfide-bound long alkyl chains. The sulfurisation experiments show that both selective preservation of algaenans and lipid and carbohydrate “vulcanisation” can be involved in the preservation of algal organic matter in marine environments.