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.     

浅析长侧链正烷基二氢化茚、烷基噻吩类化合物的地质意义

从颗石藻、球等辫金藻３００℃热模拟产物中检测出长侧链正烷基二氢化茚、烷基噻吩类化合物。二氢化茚类化合物碳数分布范围为Ｃ１３￣Ｃ２５,ｎＣ１４烷基二氢化茚的相对含量最高,没检测到茚类化合物,说明二氢化茚和茚可以源自不同的先质,生活于咸水环境的低等生物是二氢化茚类化合物的母质之一。在３００℃热解产物中检测出以ｍ／ｚ１１１和１２５为基峰的两个系列的长侧链烷基噻吩,表明在中－高盐度环境下,藻类将无机硫转化     

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”.     

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.     

腐泥煤变质系列热解色谱和氯仿沥青“A”的特点

对滕县、淄博两煤田与腐殖煤共生的不同煤级的腐泥煤进行了热解和氯仿沥青“Ａ”的族组份分析,获得如下认识：热解的结果,Ｔｍａｘ、Ｓ１、Ｓ３、Ｉｐ全部高于共生腐殖煤,Ｉｔ全部低于共生腐殖煤,Ｓ２和Ｃｐ在低煤化阶段高于腐殖煤,而中,高煤化阶段则低于腐殖煤;氯仿沥青“Ａ”都随煤级的增高而减少,腐泥煤全部高于腐殖煤,腐泥煤从低煤级到高煤级其族组份的排序从饱和烃＞非烃＞芳烃＞沥青质变化到非烃＞芳烃＞沥青质＞饱和烃;而腐殖煤族组份的排序则从沥青质＞芳烃＞非烃＞饱和烃＞沥青质。     

高温超高压模拟实验研究--Ⅱ.高温高压下烷烃产物的演化特征

对不成熟泥炭样品进行了高压（0.1～2 GPa) 、高温( 200 ℃～400 ℃）模拟实验,并对实验后样品的烷烃产物进行了分析。结果显示,同一压力条件下,温度升高,烷烃参数表现出更成熟的特征;温度较低时（200 ℃）,压力升高,烷烃参数表现出不成熟,温度较高时（400 ℃）,除个别特殊点之外,压力增大,烷烃参数愈来愈不成熟,说明温压条件都是影响有机质成熟的重要因素,压力的存在会抑制有机质的成熟作用。用模拟实验手段来探讨压力的作用和影响,具有重要的理论及实际意义。     

Study of Pyrolysis Kinetics of Asphaltenes in Silurian Oilsands in the Tarim Basin

It is a special petroleum geological phenomenon that Silurian oilsands are extensively distributed in the central and northeast Tarim basin. Some geochemical studies of the oilsands have been carried out, but there is still great controversy over the hydrocarbon-regenerating potential of oilsands and the possibility of Silurian oilsands as hydrocarbon source rocks. In this study, the kinetics of asphaltenes pyrolysis was directly used to simulate the potential of Silurian oilsands for regenerating hydrocarbons. According to the experimental results, combined with other related organic geochemical analysis, it is considered that Silurian oilsands in the Tarim basin have a high hydrocarbon-regenerating potential and are latent hydrocarbon source rocks.     

A Comparison Study on the δD Value of Polycyclic Aromatic Hydrocarbons in Hydrous Pyrolysate of Herbaceous Peat with Different Water Medium

To investigate the influence of diagenetic water media on the hydrogen isotopes of individual sedimentary aromatic compounds, a series of hydrous pyrolyses were conducted on herbaceous peat. Polycyclic aromatic hydrocarbons (PAHs) in hydrous pyrolysed samples and their hydrogen isotopic composition characteristics were studied. The aqueous medium demonstrated a significant influence on the hydrogen isotopic composition of the individual PAHs generated during pyrolysis. The results showed that the PAHs formed after pyrolysis in the presence of a saltwater medium with high δD value from a salt lake had a heavy hydrogen isotopic composition. The PAHs formed after pyrolysis in the presence of a fresh water medium with low δD value from a swamp had a light hydrogen isotopic composition. The difference in the average PAH δD value between the two hydrous experiments varied from –174‰ to –109‰, suggesting that the hydrogen isotopic composition of individual sedimentary PAHs can reflect the source of the diagenetic water medium. In addition, a comparative study found that the hydrogen isotopes of PAHs were superior to those of n-alkanes in the same sample for diagenetic water indications. The results indicated that the exchange of water-derived inorganic hydrogen and organic hydrogen was more intensive in freshwater experiments than in saltwater experiments. With an increase in the simulation temperature, the average δD value of PAHs generated in the hydrous simulation experiments showed an increasing trend, reflecting that the δD value of sedimentary PAHs formed with the participation of diagenetic water media was still closely related to the thermal maturity of organic matter. Comparative studies showed that the δD values of different types of organic compounds produced by hydrous pyrolysis of peat were in the order, PAHs > n-alkanes > methane.     

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。