用射频低温氧化法去除未熟烃源岩中的有机质方法研究

利用GP02-A高频感应加热设备产生高频磁场，等离子体在高频磁场中激活氧气形成活性氧，活性氧在低温低压下氧化烃源岩中的有机质，从而达到去除有机质并确定其含量的目的。采用射频低温氧化法对我国7个盆地未熟烃源岩进行了有机质去除的实验，结果表明，在最佳条件下用20-40h可把未熟烃源岩中的有机质去除，我国7个盆地未熟烃源岩中有机质的质量含量为1．53％～3．17％。     

有机质对未熟烃源岩低温催化混合酯水解生烃的影响

选择十六烷酸甲酯和十八烷酸甲酯组成的混合酯为模型反应物,采用不同的方法对未熟烃源岩进行有机质抽提,以连串反应的动力学模型考察抽提前后未熟烃源岩低温催化混合酯水解率及生烃率的变化,分析有机质组分对催化反应的影响.结果表明:相比于抽提有机质后的未熟烃源岩,含有有机质的未熟烃源岩低温催化混合酯的水解率和生烃率更高.     

未熟烃源岩低温催化脂肪酸酯生烃动力学研究

采用低温催化法研究未熟烃源岩催化脂肪酸酯生烃的动力学具有地质学上的实际意义。在模拟未熟油生成的地质条件下，选择十八烷酸甲酯作为模型化合物，以6种抽提有机质的未熟烃源岩作为载体，通过动力学的方法考察了未熟烃源岩矿物对脂肪酸酯生烃反应的催化作用。实验结果表明，在地质温度小于200℃的条件下，未熟烃源岩矿物催化脂肪酸酯生烃反应的活化能与碳酸盐含量、粘土总含量有一定的相关性。     

未熟烃源岩低温催化单一酯与混合酯水解和生烃反应比较

选取胜利和江汉2个油田的未熟烃源岩为催化剂,以单一的十四烷酸甲酯、十六烷酸甲酯和十八烷酸甲酯以及它们的混合酯为模型反应物,分别进行相同条件下低温催化混合酯的水解及生烃模拟实验.结果表明:江汉、胜利2种未熟烃源岩低温催化单一酯的水解反应,水解率从大到小的顺序为:十四烷酸甲酯,十六烷酸甲酯,十八烷酸甲酯,而催化混合酯水解率大小则相反.催化单一酯与混合酯的生烃反应,生烃率从大到小的顺序均为:十八烷酸甲酯,十六烷酸甲酯,十四烷酸甲酯.由于混合酯中各种酯在未熟烃源岩表面上存在着催化活性位的竞争吸附,混合脂肪酸酯的水解率及生烃率都较单一脂肪酸酯的水解率及生烃率低.     

未熟烃源岩低温催化脂肪酸酯生烃动力学研究

采用低温催化法研究未熟烃源岩催化脂肪酸酯生烃的动力学具有地质学上的实际意义。在模拟未熟油生成的地质条件下,选择十八烷酸甲酯作为模型化合物,以6种抽提有机质的未熟烃源岩作为载体,通过动力学的方法考察了未熟烃源岩矿物对脂肪酸酯生烃反应的催化作用。实验结果表明,在地质温度小于200℃的条件下,未熟烃源岩矿物催化脂肪酸酯生烃反应的活化能与碳酸盐含量、粘土总含量有一定的相关性。     

有效烃源岩的识别方法

有效烃源岩的识别和评价是含油气系统和油气成藏研究的基础。以往常用有机碳含量下限 (0 .5 % )作为烃源岩是否有效的判识标志。东营凹陷沙河街组厚达 10 0 0～ 15 0 0m的暗色泥岩的有机碳含量大于 0 .5 % ,因此长期以来人们把其作为有效烃源岩。对东营凹陷进行精细的油源对比发现 ,其有效烃源岩绝未达到 10 0 0m之厚 ,对油气藏真正有贡献的主要为沙四上和沙三下亚段有机碳含量在 1.5 %以上的烃源岩 ,它们控制了东营凹陷各亿吨级大油田的形成。因此 ,有效烃源岩下限标准的确立 ,应以研究区的实际情况而定 ,可首先通过油源对比确立有效烃源岩层段 ,然后运用测井方法删除非烃源岩夹层 ,并获取烃源岩的各项评价参数 ,从而完成有效烃源岩的识别和评价工作。     

可溶脂肪酸低温矿物催化生成甲烷的实验研究

将十八烷酸作为模型反应物 ,以改性蒙脱石、苏北和江汉油田未熟烃源岩岩样为催化剂 ,考察了在不同压力、温度下 ,脂肪酸低温催化加氢生成甲烷的能力。实验结果表明 ,温度、压力及矿物催化剂的结构对十八烷酸低温催化加氢生成甲烷有显著的影响。同时 ,在模拟地质条件下 ,未熟烃源岩中所含的可溶脂肪酸也能够生成一定量的甲烷 ,且水的存在对甲烷的生成有促进作用。     

黄河口凹陷古近系烃源岩的地球化学特征

渤海湾盆地黄河口凹陷古近系发育有3套烃源岩,分别是沙三段、沙一至二段和东三段湖相烃源岩.3套烃源岩在整个凹陷内都有分布,岩性以灰色、深灰色、灰黑色以及黑色的泥岩和油页岩为主.沙三段和沙一至二段烃源岩有机质丰度高,有机质类型好,以ⅡA型和ⅡB型为主,有机质正处于生烃的高峰阶段,这2套烃源岩是黄河口凹陷最有利的烃源岩.     

喀什凹陷侏罗系煤系烃源岩的生烃史研究

根据黄金管—高压釜封闭体系热模拟实验结果,结合古热史资料,研究了喀什凹陷侏罗系煤系烃源岩(煤和泥岩)的产气性与生烃史。研究表明,侏罗系煤和泥岩均具有较好的产气性,在中—高热演化阶段可生成较大量的天然气,且以产甲烷气为主。无论是煤,还是泥岩,喀什凹陷侏罗系烃源岩生气时问发生得晚,生气门限出现在5Ma,主生气期出现在3．5～1Ma。这种晚期生气特征为喀什凹陷天然气的晚期聚集成藏提供了较为有利的气源条件。     

新疆胜利和田探区南部下二叠统烃源岩的有机地化研究

以下二叠统克孜里奇曼组（P1k)海相碳酸盐岩为主要研究对象,对新疆胜利和田探区南部的石炭－二叠系海相烃源岩开展了系统研究。有机岩石学分析表明,该套烃源岩具有陆源和海相有机质双重输入的特点,有机质呈现偏腐殖的特征,干酪根以Ⅲ,Ⅱ型为主,与碳酸盐岩通常具有的较好有机质类型存在一定差别。有机地化分析也支持上述结论,并且指示出沉积环境并非严格的强还原环境。分析认为造成有机质类型较差的原因主要有3种,即陆源有机质输入、宏观藻类的贡献以及沉积环境充氧造成的有机质氧化。根据以上有机岩石学和有机地化分析的结果,结合碳酸盐岩孔隙度低,排烃较晚的特点,确定该套烃源岩以生成轻质烃类为主。塔西南地区广泛发育有石炭－二叠系海相碳酸盐岩沉积,该套气源岩对于区内天然气的勘探具有一定的石油地质意义。     

Catalytic decarboxylation of fatty acid by iron-containing minerals in immature oil source rocks at low temperature

The catalytic activities of seven immature source rocks in China on fatty acid decar-boxylation for generating hydrocarbons have been evaluated by determinating the CO2 content from decarboxylation reaction of stearic acid. It has been found that the catalytic activities of immature source rocks mainly depend on the structure type of the minerals. In general, the catalytic activities of carbonates are higher than those of clays at low temperature. The higher its iron content, the higher the catalytic activity of carbonate.     

Simulation experiments for evolution of fatty acids in immature source rocks

The anhydrous, hydrous and bitumen-extrac- ted simulations were carried out for the immature source rocks from the Liaohe sag. It has been shown from the result that with increasing temperature in simulation experiments, the fatty acids content decreased at first and then increased. The decrease of fatty acids in immature rocks is presumably related to alkanes generation in immature oils, whilst the increase may be related to the fact that some additional fatty acids are generated from kerogen and the tightly bound fatty acids in kerogen are released as bound fatty acids in kerogen and unbound fatty acids in bitumen. The fact that the bitumen generated from kerogen contains fatty acids has demonstrated that some bound and tightly bound fatty acids in kerogen can be transferred into bitumen. The preferential fatty acids in the immature source rocks are found to be mono-carboxylic acids with longer chains, whilst krogen contains relatively more di-carboxylic acids. It has been found that the fatty acids in immature source rocks can be changed from that with more longer chains to that with more shorter chains when evolution extent has been increased. Based on simulation results and the fact that the majority of fatty acids in immature oils are those with longer chains, it is inferred that the contribution of fatty acids to forming alkanes in immature oils mainly takes place at the evolution stage with R₀ <0.6%. The simulation experiments have also demonstrated that H₂O could promote the generation of fatty acids with more di-carboxylic acids and delay alkanes formation from fatty acids.     

The occurrence of fatty acids in immature source rocks and their distribution characteristics

The fatty acids in extractable bitumen and kerogen of immature source rocks of the Liaohe Basin and Jiyang sag were investigated in this study. The result showed that the bitumen fatty acids were mainly associated with non-hydrocarbon fraction and that the kerogen fatty acids with some tightly bound fatty acids were mainly bounded in a net structure of kerogen by ester bonds. For the investigated source rocks, the fatty acids in bitumen, bound fatty acids and tightly bound acids in kerogen ranged in 0.01%—0.073.9%, 0.005%— 0.045 5% and 0.005%— 0.010% respectively. Among the fatty acids analyzed in this study, mono-carboxylic acids, a , w -di-carboxylic acids and hydroxy acids accounted for 70%—100%, 0%—30% and <10% respectively. It was also found that the mono-carboxylic acids with longer chains mainly existed in bitumen, and that the a , w -di-carboxylic acids and hydroxy acids mainly existed in kerogen. From above, it was assumed that the mono-car- boxylic acids in bitumen might have played an important role in the hydrocarbon generation from fatty acids in immature source rocks.     

歧口凹陷沙一段低熟烃源岩评价

利用烃源岩有机质丰度、生排烃特征、发育古环境、有机岩石学及原油特征等手段,探讨歧口凹陷沙一段低熟烃源岩生烃、排烃特征。研究结果表明,歧口凹陷沙一段低熟烃源岩有机质丰度高、类型好,具有集中排烃、高效排烃的特点。沙一下段烃源岩发育的环境主要为干旱气候下的咸水环境。藻类及显微组分中的矿物沥青基质是低熟烃源岩形成低熟油气的物质基础。歧口凹陷存在大量未熟-低熟的原油。     

Quantification and implications of two types of soluble organic matter from brackish to saline lake source rocks

Two types of soluble organic matter, the free and adsorbed, were obtained and quantified from the brackish to saline lake source rocks. The adsorbed type was extracted with chloroform, solvent mixtures of methanol：acetone：chloroform （MAC） and CS2：N-methyl-2-pyrrolidinone （CSz/NMP）. The total amounts of the two types of soluble organic matter from some immature source rocks are 〉830 mg/g TOC, more than 63% of the total organic matter in these samples. This result indicates that the majority of the organic matter in the immature source rocks in the brackish to saline lake basin is soluble, and is significant for study of petroleum formation and helpful for petroleum exploration in the brackish to saline lake basin.