Similarities and differences in hydrous pyrolysis of biomass and source rocks

In laboratory simulation of oil generation, products from closed systems pyrolysis of immature source rocks in the presence of water gives the closest match to petroleum compositions observed in nature. Fresh biomass can also be converted to fluids by pyrolysis, but in the absence of the sedimentary diagenetic transformations, the initially much higher oxygen content gives high yields of oxygen containing products. In this work, the reactions that occur during hydrous pyrolysis of a Kimmeridge source rock, a brown coal and two polymeric waste materials from alginate production are compared in terms of quantities of the main products and kinetic models of the reaction systems. The biomass pyrolysis and the simulated maturation are described in similar reaction networks. Conversion of biomass to fluids occurred with reaction networks and activation energy distributions comparable to the brown coal, while for the Kimmeridge source rock reactions a simpler reaction network could be used. The biomass samples gave a high degree of conversion to fluid products, and higher yields of bitumen than the coal.     

Effects of base catalysis on the product distribution from pyrolysis of woody biomass in the presence of water

Previous work has shown that woody biomass can generate oil-like products during hydrous pyrolysis. However, the yield of extractable organic matter is rather small, and the proportion of coke is high. In order to increase the oil yield and decrease the coke generation, experiments with added base catalysts have been made. NaOH was chosen as the catalyst. Experimental design is used to investigate the effects of variable experimental conditions during pyrolysis. The results are compared with similar experiments without a catalyst, and show a general decrease in coke formation and increase in the extractable organic matter with a dominance of polar compounds. The variable with the largest effect on yields is the amount of water, while pyrolysis temperature and the amount of starting material have minor effects.     

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     

Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis

An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330°C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH₂ and HI/LiAlH₄) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis–GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260°C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak carbon–heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220°C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments.     

南海长链烯酮化合物的检测及U37^k值的应用

首次系统地在南海大面积站位中检测出长链烯酮化合物。通过长链烯酮指标Ｕ３７ｋ与实测表层海水温度（ＳＳＴ）的对比研究,发现海洋沉积物样品在室温下长期（１７ａ）密封保存,长链烯酮指标Ｕ３７ｋ值无明显变化。Ｕ３７ｋ值在南海海区指示的表层海水温度与季节有关,主要反映秋、冬两季,即１０月至次年３月间的ＳＳＴ。     

珠江口盆地Site4B柱状沉积物中长链烷基二醇和酮醇类化合物的检出及意义

珠江口盆地Site4B沉积物中（65~300 cm）检出了1,15-C30（ω16）和1,15-C32（ω18）烷基二醇和酮醇,总的长链烷基二醇和酮醇含量分别为0.026～4.373 μg/g干沉积物和0.005～1.549 μg/g干沉积物。沉积物剖面上检测到的1,15-C30烷基二醇（-26.6‰±0.9‰）相对于来自陆源高等植物的C30直链烷基醇（-32.8‰±1.5‰）较正的碳同位素特征反映了这类化合物可能不是来自陆源高等植物;同时沉积物中未检出在黄绿藻中相对长链烷基二醇和酮醇更丰富的甾醇,且沉积物浅表层中（0~65 cm）未检出长链烷基二醇和酮醇类化合物,表明现今沉积物中几乎没有黄绿藻的贡献,和沉积物所处的寡营养盐（不适宜藻类生长发育）的陆坡位置相吻合。沉积物中1,15-C30烷基二醇（-24.6‰～-28.4‰）和海洋细菌来源的短链脂肪酸 (-25.5‰～-28.6‰)具有相似的碳同位素组成,表明了海洋细菌是其可靠来源。Site4B沉积物中1,15-C30和1,15-C32烷基酮醇和二醇具有非常好的相关性,表明了它们可能来自相同的生物来源或者来自相关性较好的不同生源,而不是通过对应的二醇氧化生成,因为在65~95 cm的氧化环境中酮醇比例没有明显增高。Site4B沉积物中二醇参数和酮醇参数的变化非常相似,结合含量分布特征反映了古海水温度以及淡水入侵的双重影响,即较高的二醇参数及较高的二醇含量和较低的二醇参数及较低的二醇含量都可能反映了古海水温度是主要影响因素;而较低的二醇参数及较高的二醇含量则可能反映了淡水的侵入是主要影响因素。     

青藏高原湖泊长链不饱和烯酮研究现状及展望

陆地温度的定量重建一直是古气候研究领域最具挑战性的工作之一。古温度定量记录不仅可以为气候模式的输出结果提供验证,同时也可为全球变化背景下过去温度提供参考。长链不饱和烯酮化合物的发现及有机地球化学分析手段的提高为古温度定量重建提供了可能。新生代以来青藏高原的隆升对东亚环境演变产生显著影响,其在全球气候变化研究中具有重要位置,然而高质量的古气候定量记录在青藏高原仍十分缺乏,极大限制了对高原气候变化机制的深入理解。近年来利用长链不饱和烯酮指标重建水体温度在海洋及陆地湖泊环境得到了广泛应用。青藏高原湖泊具有分布广、数量多等特点,是利用长链烯酮开展古气候定量重建的理想区域。本文通过对已发表的湖泊长链烯酮研究手段及相关成果进行总结,以青藏高原湖泊烯酮研究现状为背景,对高原烯酮研究提出展望。     

冲绳海槽长链二醇生物标志物对中晚全新世黑潮变化的指示意义

长链二醇（LCDs）是一类微藻生物标志物,在海洋沉积物中除了能够指示其生物来源,近年来的工作还表明它们能够很好地用于示踪表层海水温度（SST）和营养盐。本文对冲绳海槽北部OTK-6站位的1根中晚全新世柱状沉积物（长度468cm）进行了长链二醇的提取分析,重建了7 ka B.P.以来的表层海水温度和营养盐变化历史,并与前人的黑潮指标变化进行对比。结果显示,在本研究区基于长链二醇的SST指标可能反映的是年均但略偏暖季的温度,其变化曲线与营养盐指标的变化曲线呈反向变化。而且上述温度和营养盐变化历史与前人给出的黑潮强弱变化历史对应较好,表现出黑潮增强时,SST温度升高,营养盐含量降低,与黑潮水的高温寡营养的特点一致。本文结果显示,在6.0~5.2 ka B.P.、4.2~3.5 ka B.P.、2.5~2.1 ka B.P.、1.8~1.4 ka B.P.以及1.1~0.8 ka B.P.前后黑潮对研究区域的影响加强。因此,认为基于长链二醇的温度和营养盐指标有潜力成为重建古黑潮演变的新型代用指标。

     

Evaluation of the petroleum composition and quality with increasing thermal maturity as simulated by hydrous pyrolysis: A case study using a Brazilian source rock with Type I kerogen

Hydrous pyrolysis (HP) experiments were used to investigate the petroleum composition and quality of petroleum generated from a Brazilian lacustrine source rock containing Type I kerogen with increasing thermal maturity. The tested sample was of Aptian age from the Araripe Basin (NE-Brazil). The temperatures (280–360 °C) and times (12–132 h) employed in the experiments simulated petroleum generation and expulsion (i.e., oil window) prior to secondary gas generation from the cracking of oil. Results show that similar to other oil prone source rocks, kerogen initially decomposes in part to a polar rich bitumen, which decomposes in part to hydrocarbon rich oil. These two overall reactions overlap with one another and have been recognized in oil shale retorting and natural petroleum generation. During bitumen decomposition to oil, some of the bitumen is converted to pyrobitumen, which results in an increase in the apparent kerogen (i.e., insoluble carbon) content with increasing maturation.The petroleum composition and its quality (i.e., API gravity, gas/oil ratio, C₁₅₊ fractions, alkane distribution, and sulfur content) are affected by thermal maturation within the oil window. API gravity, C₁₅₊ fractions and gas/oil ratios generated by HP are similar to those of natural petroleum considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. API gravity of the HP expelled oils shows a complex relationship with increasing thermal maturation that is most influenced by the expulsion of asphaltenes. C₁₅₊ fractions (i.e., saturates, aromatics, resins and asphaltenes) show that expelled oils and bitumen are compositionally separate organic phases with no overlap in composition. Gas/oil ratios (GOR) initially decrease from 508–131 m³/m³ during bitumen generation and remain essentially constant (81–84 m³/m³) to the end of oil generation. This constancy in GOR is different from the continuous increase through the oil window observed in anhydrous pyrolysis experiments. Alkane distributions of the HP expelled oils are similar to those of natural crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. Isoprenoid and n-alkane ratios (i.e., pristane/n-C₁₇ and phytane/n-C₁₈) decrease with increasing thermal maturity as observed in natural crude oils. Pristane/phytane ratios remain constant with increasing thermal maturity through the oil window, with ratios being slightly higher in the expelled oils relative to those in the bitumen. Generated hydrocarbon gases are similar to natural gases associated with crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous, with the exception of elevated ethane contents. The general overall agreement in composition of natural and hydrous pyrolysis petroleum of lacustrine source rocks observed in this study supports the utility of HP to better characterize petroleum systems and the effects of maturation and expulsion on petroleum composition and quality.     

长链烷基二醇及其指标在南海北部粤东沿海上升流地区的环境指示

本文以南海北部粤东沿海夏季上升流三个短柱状岩心为研究对象,通过二醇化合物分布分析测试和二醇环境参数的定量化重建,初步探讨了过去80年来海水表层温度(SST)、上升流活动和沉积环境演变过程及其交互关系。二醇温度指标(LDI)在粤东沿海地区较好地指示了年均SST,在三个岩心中均显示了整体增加的分布特征和相似的多年尺度变化趋势。此外,LDI SST和二醇参数2具有非常好的线性关系(R2=0.85,n=49),其整体分布、多年尺度变化均和ENSO旋回一致,并且大部分高/低值和ENSO暖/冷年、南海夏季风强/弱年具有很好的对应关系,表明了二醇参数2可以作为粤东上升流强度变化(多年/单年尺度)的替代性指标。而1,14 二醇含量和ENSO指标在多年尺度上显示了相似的波动特征,但大部分高/低值和南海夏季风指数、ENSO指标呈反相分布,说明了仅用1,14 二醇含量不可反演粤东上升流。据此,利用二醇参数2初步重建了过去80年来粤东上升流演变信息：上升流强度整体上显示加强的分布趋势,大体上呈约2~5年周期变化。此外,三个岩心中1,15 C30(二醇/二醇+酮醇)比值和二醇参数2在整体上和多年尺度上均呈现相反的分布特征,可能与上升流活动导致的1,15 C30二醇母源再悬浮再氧化有关,而普遍较高的1,15 C30二醇比值(≥0.82)反映的强还原环境则和上升流地区水体中含氧量普遍偏低相关。