油气生成热模拟实验研究进展

作为研究油气地球化学的一种重要手段－－热模拟被愈来愈广泛地应用。介绍了不同时期油气生成模拟实验研究的状况，阐述了模拟实验已解决的和尚存在的问题，进而指出了其发展趋势和应开展的工作。     

Pyrolysis-combustion C dating of soil organic matter

Radiocarbon (¹⁴C) dating of total soil organic matter (SOM) often yields results inconsistent with the stratigraphic sequence. The onerous chemical extractions for SOM fractions do not always produce satisfactory ¹⁴C dates. In an effort to develop an alternative method, the pyrolysis-combustion technique was investigated to partition SOM into pyrolysis volatile (Py-V) and pyrolysis residue (Py-R) fractions. The Py-V fractions obtained from a thick glacigenic loess succession in Illinois yielded ¹⁴C dates much younger but more reasonable than the counterpart Py-R fractions for the soil residence time. Carbon isotopic composition (δ¹³C) was heavier in the Py-V fractions, suggesting a greater abundance of carbohydrate- and protein-related constituents, and δ¹³C was lighter in the Py-R fractions, suggesting more lignin- and lipid-related constituents. The combination of ¹⁴C dates and δ¹³C values indicates that the Py-V fractions are less biodegradation resistant and the Py-R fractions are more biodegradation resistant. The pyrolysis-combustion method provides a less cumbersome approach for ¹⁴C dating of SOM fractions. With further study, this method may become a useful tool for analyzing unlithified terrestrial sediments when macrofossils are absent.     

Stability and hydrogenation of polycyclic aromatic hydrocarbons during hydropyrolysis (HyPy) – Relevance for high maturity organic matter

A series of hydropyrolysis (HyPy) experiments have been conducted on a small suite of authentic polycyclic aromatic hydrocarbons (PAHs: coronene, pyrene and perylene) to investigate the HyPy behaviour of these PAHs. This information may help in the interpretation of the structural significance of aromatic HyPy products, often detected in high abundance, from high maturity kerogens. The PAHs were separately treated by HyPy and were all susceptible to some extent of hydrogenation. Perylene also decomposed into low molecular weight aromatics (e.g. methylbiphenyls). Structurally, perylene is much less stable than the more condensed PAHs coronene and pyrene. The total product concentrations (wt% of starting PAH) from all HyPy experiments were consistently less than 100 wt%, probably due to either the condensation of semi-volatile products on walls of the transfer line prior to reaching the HyPy trap or the inefficient cold trapping of highly volatile products. Hydrogenation of PAHs was prevalent and was found to be significantly influenced by the addition of a Mo-S based catalyst and potentially the C/Mo ratio, but largely independent of the two final temperatures used (520 °C and 550 °C). The fully aromatised and hydrogenated products for any stable ring system may provide a general indication of the size distribution of aromatic units within the kerogen structure.     

Inside amber: New insights into the macromolecular structure of Class Ib resinite

Class Ib resinites are the most common subclass of amber and are found throughout the world. They have a macromolecular structure based on co-polymerized communic acid, communol and biformenes. Because this class of resinite does not contain succinic acid, crosslinking of the polymer through esterification of communol moieties has never been theorized. Analysis of Class Ib resinites from Grassy Lake and Cedar Lake in western Canada was performed using pyrolysis–gas chromatography–mass spectrometry with in situ hexamethyldisilazane derivatization, using a thermal separation probe to perform the pyrolysis and sample introduction. This has allowed larger, more complex fragments to be released from the polymer matrix than previously possible using instantaneous pyrolysis methodologies. The results show for the first time that Class Ib resinite can undergo self-crosslinking between the communol and communic acid moieties in the polylabdane matrix. The chromatographic results also show that a portion of the monoterpenes and non-polymerizable diterpenes in the resinite are bound to the polymer matrix and not fully occluded as was previously theorized. Fourier transform infrared (FTIR) spectra of the resinites are presented and a more accurate spectral interpretation is proposed, based on the chromatographic results.     

TSR对碳酸盐岩中沥青生烃影响的模拟实验

利用地层孔隙热压生排烃模拟仪实验装置,对采自四川盆地西北部广元矿山梁地区下寒武统具高有机质含量、高氢指数和低成熟度特征的固体沥青,开展了模拟地层条件下的"沥青+白云岩+去离子水"(系列A)和"沥青+白云岩+硫酸镁+去离子水"(系列B)生排烃实验。结果表明,这两个系列的气体产率具有较大差异,其中,加入硫酸镁的系列(系列B)发生了热化学硫酸盐还原反应(TSR),使气态烃和非烃气体的产率增大,同时也加速了重烃气体的裂解,导致重烃气体大量裂解的温度降低。     

油页岩原位裂解用注热管柱数值传热模拟与试验研究

油页岩作为一种非常规油气资源,有望成为石油的替代品。油页岩原位裂解技术对环境污染小,生成的油页岩油油品好,具有良好的开发前景。在原位裂解过程中,减少注热过程中的热量损失具有十分重要的意义,因此本文将对保温注热管柱的传热特性进行数值模拟和试验研究。通过传热学计算分析,保温注热管柱设计为外径?32mm的钢管,外层缠绕共计24mm的纳米保温材料。数值分析表明氮气流量越大,注热管柱出口温度达到稳定的时间越短,稳定温度也越高;当管柱氮气入口温度为500℃时,管柱出口温度在一定注气时间后均可达到400℃以上。在农安油页岩原位裂解先导试验工程中对注热管柱进行野外试验,管柱达到注热保温效果,井底温度达到设计温度,最终成功获得油页岩油。     

Aromaticity and degree of aromatic condensation of char

The aromatic carbon structure is a defining property of chars and is often expressed with the help of two concepts: (i) aromaticity and (ii) degree of aromatic condensation. The varying extent of these two features is assumed to largely determine the relatively high persistence of charred material in the environment and is thus of interest for, e.g., biochar characterization or carbon cycle studies. Consequently, a variety of methods has been used to assess the aromatic structure of chars, which has led to interesting insights but has complicated the comparison of data acquired with different methods. We therefore used a suite of seven methods (elemental analysis, MIR spectroscopy, NEXAFS spectroscopy, ¹³C NMR spectroscopy, BPCA analysis, lipid analysis and helium pycnometry) and compared 13 measurements from them using a diverse sample set of 38 laboratory chars. Our results demonstrate that most of the measurements could be categorized either into those which assess aromaticity or those which assess the degree of aromatic condensation. A variety of measurements, including relatively inexpensive and simple ones, reproducibly captured the two aromatic features in question, and data from different methods could therefore be compared. Moreover, general patterns between the two aromatic features and the pyrolysis conditions were revealed, supporting reconstruction of the highest heat treatment temperature (HTT) of char.     

Pyrolytic and spectroscopic study of a sulphur-rich kerogen from the “Kashpir oil shales” (Upper Jurassic, Russian platform)

The kerogen of an organic-rich sample, termed f top, from the Gorodische section (Russian platform) was studied using a combination of microscopic, spectroscopic and pyrolytic methods so as to examine its chemical structure, source organisms and formation pathway(s). This kerogen, which is mainly composed of orange gel-like, nanoscopically amorphous organic matter, exhibits a relatively high aliphatic character; organic sulphur is mainly present as di(poly)sulphides and alkylsulphides. The f top kerogen was chiefly formed via intermolecular incorporation of sulphur in algal or cyanobacterial lipids and carbohydrates. However, its formation also involved oxidative condensation via ether linkages. Comparison of f top sample with other S-rich kerogens points to a closer similarity with Monterey kerogens rather than with a kerogen from the bituminous laminites of Orbagnoux.