煤岩显微组分热解气相色谱特征与化学结构剖析

煤结构是目前地球化学研究领域中的一个难点，但却具有极其重要的理论及实际意义，本文采用分步热解气相色谱技术将树皮体，镜质体和丝质体分解为分子量较小的可测定的有机化合物，在此基础上，据不同温度下热解产物的组成特征来还原显微组分的化学结构，实验结果表明，煤显微组分主要由四大类官能团组成，一是热稳定性较低的NOS杂原子官能团；二是脂族（脂链、脂环）结构；三是苯、烷基苯（甲苯、二甲苯）、萘等芳香族化合物，四是热稳定性很高的难以分解的稠环芳烃。上述四类化合物集中于显微组分的不同结构简单中，树皮体和镜质体结构单元外侧主要由热稳定性较低的杂原子化合物以及分子量较小的苯和烷基苯组成，而丝质体结构单元外侧则主要以短链脂族结构为主，三组分结构核部由热稳定性很高的难以分解的稠环芳烃组成。连结核部稠环芳烃与结构单元外侧杂原子等官能团的主要是热稳定性较高的脂链结构，煤显微组分热成烃主要按结构中各官能团键的强弱随热演化程度的加深依次脱除，生成油气，基本上属平行独立依次反应机制，亦“官能团脱除型”，此外，还包括少量的长链脂族结构裂解为短链脂肪烃的“解聚”过程。     

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.     

Characterisation of brown coal humic acids and modified humic acids using pyrolysis gcms and other techniques

It has been proposed that Victorian brown coal can be considered as a two-component structure — a lignocellulosic “host”, containing various amounts of weakly bound or entrapped “guest” material together with very small amounts of inorganic and/or mineral matter. The latter predominantly consists of wax esters and/or terpenoid material. In this paper we describe attempts to gain structural information regarding the more complex, “host” component of the coal. Our initial model compound has been humic acid that can be readily obtained from the coal by alkaline extraction. It has been found that “pure” humic acid, free from material associated with the “guest” components of the coal, can be obtained by a highly selective, low-yielding alkaline extraction. This humic acid has been studied by nmr spectroscopy and pyrolysis gas chromatography-mass spectroscopy (py-gc/ms). The products arising from py-gc/ms have been compared with those obtained from similar pyrolysis of whole coals. Alkylation of humic acids using alkyl halides in the presence of base has been successfully carried out and reactivity of the resulting materials compared with those of the parent coal and humic acid.     

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.     

Importance of the oxidation/maturation pair in the evolution of humic coals

The natural thermal evolution of type III coals (Humic origin) is expressed during diagenesis by a loss of oxygen as CO₂ and H₂O. Other phenomena such as oxidation can cause extensive geochemical modifications and may complicate the effects of simple maturation.Humic coals from the Jurassic in southeastern Utah were studied by elemental analysis, Rock-Eval pyrolysis and infrared spectroscopy. In a van Krevelen diagram (atomic H/C vs atomic O/C), the samples fall within the envelope defined by 860 reference humic coals covering the entire range of diagenesis. Nevertheless, various criteria (geochemical, petrographic, geological and microscopic) cast doubt upon the interpretation that such a distribution of coal composition results from thermal maturation.The same criteria indicate the intervention of redox phenomena. Comparison of our results with those from artificial and natural oxidation shows that these coals were subjected to an oxidation process different from ordinary late alteration. This process was probably due to circulation of highly oxidizing saline water causing oxygen fixation and the transformation of carboxyls into carboxylate anions. The cations that were fixed are oxygenated and certainly contain calcium, but also uranium and perhaps several other cations (V, Mo, Fe...). Emphasis is placed on possible mechanisms that cause such phenomena.     

Pyrolysis of immature Torbanite and of the resistant biopolymer (PRB A) isolated from extant alga Botryococcus braunii. Mechanism of formation and structure of torbanite

Immature Torbanite and the resistant biopolymer (PRB A) isolated from extant B. braunii were previously compared using bulk spectroscopic methods. In the present work, analysis of 400°C pyrolysis products and pyrolysis residues provided further information on their structure and possible relationships. It appears that such polymers are based upon unbranched, saturated, cross-linked hydrocarbon chains up to C₃₁. In addition to these bridging structures, a substantial part of the alkyl chains is singly bound, as esters of unbranched, saturated or cis unsaturated, even fatty acids. These esters are sterically protected, against chemical degradations, by the network of the bioand geopolymer.Quantitative and qualitative observations derived from 400°C pyrolysis confirm that the chemical structure of PRB A and immature Torbanite are closely related. The pyrolysis residues show a similar evolution and numerous common features are noted, with respect to the nature and the distribution of the major constituents of the pyrolysates (hydrocarbons and fatty acids). Accordingly, Botryococcus provides what seems to be the first example of a close structural relationship between a biopolymer produced in large amounts by an extant alga and the geopolymer of an immature kerogen. The essential role of PRB A in Torbanite formation is ascertained. Moreover, it is found that the resistant biopolymer does not undergo important structural changes during the first stages of diagenesis. Thus, owing to steric protection, the esters of immature Torbanite show a distribution quite close to the one of PRB A esters, with exclusively even constituents and a large contribution of unsaturated acids.Recent observations pointed to the possible genesis of some algal kerogens principally by selective preservation of resistant macromolecules. Such a type of formation is clearly predominant in Torbanite, where the bulk of the fossil organic matter corresponds to a selectively preserved and weakly altered, resistant biopolymer, while incorporation of lipids into the kerogen structure during diagenesis seems to play a minor role.     

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.     

Artificial Maturation of Organic Matter from Recent Venezuelan Sediments

Laboratory simulation of the catagenesis of organic matter in sedimentary rocks has been used to provide an understanding of the processes involved in petroleum generation. Several of these studies have focused on the thermal evolution of organic matter (OM) present in Recent sediments. This study examines the geochemical characteristics and experimental thermal evolution of primary organic matter from two organic facies that are thought to be major contributors to Venezuelan hydrocarbon source rocks. A third facies, generally considered unimportant for petroleum formation, is used to contrast the experimental results. Hydrous pyrolysis maturation experiments were performed for three intermediate temperatures. The products of the final 330°C stage are shown in this paper because they best illustrate the changes in the OM during catagenesis. Results from the hydrous pyrolysis experiments show that at 280°C and higher all three samples yield liquid hydrocarbons similar in composition to natural crudes and the transformed organic matter is similar to kerogen that occurs in natural source rocks. Chromatograms from the saturated fraction of extracts at 330°C are similar to natural crudes with respect to n-alkane distribution and abundance of beta; and beta;alpha; hopanes. The only difference seems to be the relative abundance of 22R over 22S isomers, which indicates immature oil. This is in contrast to indications from the R _o and T _max parameters measured on the accompanying kerogen.