松辽盆地优质烃源岩含水生排油模拟实验

为了搞清松辽盆地优质烃源岩的生排油机理,为油气资源评价提供可靠参数,对松辽盆地优质烃源岩进行了含水生排油模拟实验.实验结果表明:优质烃源岩在低熟条件下可以排出少量油,排出量只占总排油量的10%;优质烃源岩在主要生排油阶段具有较高的排油效率,一般在60%～80%;模拟实验排出的油与松辽盆地主要油层中已发现的原油化学性质一...     

湖相烃源岩排烃差异性模拟研究——以东营凹陷古近系沙三段为例

从岩石结构和有机质特征来说,烃源岩均具有很强的非均质性,以东营凹陷沙三段的块状泥岩、纹层泥岩和油页岩为例,采用烃源岩全岩(未粉碎)进行模拟实验,结合地质剖面,分析了该区烃源岩的排烃机理及其差异性.结果表明,生烃作用是烃源岩排烃的根本原因,早期是富集液态油的主要阶段,当液态油富集达到一定程度时开始排烃;主要的排烃期出现在液态油生成高峰及其之后,当液态油中的总烃(尤其是轻质烃类)大量生成时,排烃效率明显增大.各种原因形成的微层理和微裂缝是油气运移的优势通道.3类烃源岩的排烃效率明显不同,这与烃源岩的结构及演化阶段有关.     

东营凹陷烃源岩排油机理

东营凹陷主力烃源岩生成的油气主要以油相形式从烃源岩中排出,水溶相是未熟油-低熟油初次运移的主要形式,在高成熟阶段,气溶相则为主要运移形式.幕式排油是烃源岩系统演化过程中的一种重要排油方式,此时烃类以混合相形式运移.虽然东营凹陷烃源岩系统在一定时间和空间内具有相对滞排特征,但滞排使超压得到积累和"幕式"释放,因而厚层烃源岩仍具有较高的排油效率,其滞排系数(残留烃与生烃量比值)基本小于0.4.     

辽河油田大民屯凹陷下第三系生油岩排烃研究

采用高温高压半封闭实验体系,对大民屯凹陷下第三系生油岩进行了排烃热模拟实验,结果表明制约生油岩排烃量的因素是有机质丰度,而制约生油岩排烃效率的因素则是有机质类型。排烃作用对原油族组成烷烃和非烃和沥青质的含量影响较大,对芳烃含量影响较小。两类生油岩的排烃模式均具有无突发性排油高峰的特征。     

不同类型优质烃源岩生排油气模式

利用地层孔隙异常压力热模拟实验分别对硅质型、钙质型与粘土型优质烃源岩进行分析,生排油气模拟结果表明:(1)成熟早中期硅质型优质烃源岩排油量与排油效率最高,早期主要以重质油排出为主,排油效率高达50%左右;钙质型优质烃源岩次之,排烃效率一般在30%左右;粘土型优质烃源岩排油效率一般只有4%~11%。(2)在成熟中晚期,硅质型优质烃源岩排油效率最高,但是钙质型烃源岩增加迅速达65%,粘土型烃源岩增加不明显。(3)成熟晚期—高成熟阶段,硅质型和钙质型优质烃源岩排油效率变化不明显,而粘土型烃源岩排油效率则从20%迅速增加到90%。硅质型、钙质型和粘土型优质烃源岩生排油气模式之间最大的差异是它们在成熟早中期排油效率和排油量不同。      

北部湾盆地流二段不同类型烃源岩生排烃效率与成藏贡献对比北大核心CSCD

北部湾盆地目前的油气储量发现主要集中在涠西南和乌石凹陷这两个勘探成熟区,钻井揭示其主力烃源岩为流二段半深湖—深湖相烃源岩,包括泥岩、页岩和油页岩等3种类型。本文主要针对这两个成熟区14口井的3种类型烃源岩的岩心、岩屑及13个典型油田的原油共计173个样品进行了系统采集和分析测试,利用生排烃热模拟实验和混源油人工配比实验等手段,开展了3种类型烃源岩的生排烃效率及其对13个典型油田的成藏贡献定量对比分析。结果表明,流二段油页岩有机质丰度高、类型好,生烃潜力明显优于泥岩和页岩,是该盆地最优质的烃源岩;3种类型烃源岩的生排烃效率由高到低依次为油页岩、页岩和泥岩,其中油页岩的生油效率和排油效率最高,分别是泥岩的5.2倍和3.4倍;流二段油页岩对该盆地成熟区13个典型油田的油源贡献率超过70%,是油气成藏的主力烃源岩,因此在新区勘探潜力评价中应高度重视油页岩的分布预测及资源潜力评价。     

实验方法评价松辽盆地烃源岩的生排烃效率

针对烃源岩生排烃效率评价现有方法的不足和第四次油气资源评价研究的需要,基于模拟地质条件的最新生排烃实验平台,以白垩系烃源岩为例,开展了松辽盆地烃源岩生排烃条件和过程的模拟实验。结合包括轻烃在内的产物计量方法探索,对实验产烃量进行计量;通过实验产物的H/C原子比数据,对干酪根热成熟度进行标定,获得实验点所对应的地质RO值;从而实现了对松辽盆地白垩系烃源岩在各热演化阶段的生排烃效率厘定。结果表明,轻烃在总烃中的含量为5%~29%,并有随实验热演化程度升高的特征,在生油高峰期的轻烃含量约为25%,从而弥补了传统实验和利用岩心残留烃分析排烃效率方法中缺少轻烃组分的缺憾;通过生排烃效率曲线显示,松辽盆地白垩系烃源岩的最大生油效率为680mg/gTOC,生油高峰期对应的绝对排烃效率为57%。对压力的影响分析认为,压力确实影响热成熟演化,在生油阶段对RO的抑制约为0.2%;压力的释放促进排烃,是导致岩心滞留烃量降低和轻烃散失的主要原因,仅轻烃散失造成的生油高峰期绝对排烃效率偏差值就达18%。常规方法低估了地质实际的滞留烃量,深层找气的前景乐观。     

大港油田孔南地区烃源岩生排烃模拟试验

黄骅坳陷孔南地区是我国较早发现未熟-低熟油地区之一,为了进一步研究其烃源岩生、排烃特征,为未熟-低熟油的研究和资源评价提供支持,对该区主要生油层孔二段泥岩和次要生油层沙一下段页岩进行了热压模拟试验,并在此基础上编制了二类烃源岩生、排烃模式.模拟研究表明:这二类烃源岩都有明显的早期生、排烃的特征,且生排、烃潜力大,说明该区烃源岩具备形成未熟-低熟油的能力,具有良好地勘探前景.     

海相不同类型烃源岩生排烃模式研究

在海相烃源岩研究的基础上,筛选出青藏高原中生界和冀北地区上元古界未成熟—成熟海相不同类型烃源岩 10 个样品为代表,进行热压模拟试验,创建了海相3种类型干酪根和4种主要岩类的17种原始和再次生排烃模式。提出了海相烃源岩从Ⅰ型干酪根到Ⅱ₁型到Ⅱ₂型再到固体沥青,生排油、烃气和总生烃量逐渐变低,油质逐渐变轻,气逐渐变干,生烃速率也逐渐减小;从富烃页岩到富烃泥灰岩到富烃灰岩再到固体沥青,排油效率逐渐增加,总生排烃量和生烃速率具有逐渐减少的趋势,生烃气占总烃比例则从固体沥青到富烃页岩到泥灰岩到灰岩逐渐增加;从海相富烃源岩到低有机质含量的碳酸盐岩或随着有机质丰度的降低(TOC 0.2%到1.0%),生排油、烃气量和总生烃量及生烃速率逐渐变小,生烃气占总烃比例逐渐增加。      

鄂尔多斯盆地长7段泥页岩层系排烃效率及其含油性

泥页岩层系的排烃效率是当前页岩油气研究领域关注的重点问题之一,也是评价页岩油气资源潜力的关键参数。以鄂尔多斯盆地延长组长7段泥页岩层系为研究对象,通过系统地球化学分析,揭示了长7段泥页岩层系的排烃效率并探讨了泥页岩层系中不同岩性的含油性及其页岩油意义。中等成熟度阶段（R_o=0.8%）,Ⅰ型有机质泥页岩的排烃效率在33%~37%,Ⅱ型排烃效率在16%~26%。成熟度较高阶段（R_o=1.1%）,Ⅰ型有机质泥页岩的排烃效率在64%~67%,Ⅱ型排烃效率在54%~58%。在综合考虑不同类型岩性的含油性、滞留油族组分特征、气油比及滞留油流动性等地质因素后认为,成熟度较高的长7段泥页岩层系中（R_o=1.1%）游离烃含量和OSI指数高的砂岩段和粉砂质泥岩段等可作为页岩油勘探开发的有利目标。游离烃含量和OSI指数较高的块状泥岩段可作为页岩油勘探点潜在目标。黑色页岩段（或纯页岩段）因受若干地质因素的影响,可能会制约其成为研究区内页岩油勘探的有效目标。块状泥岩段可作为页岩油勘探的潜在目标;而黑色页岩（或纯页岩段）因受若干地质因素的影响,可能会制约其成为研究区内页岩油勘探的有效目标。     

DISSOLUTION OF COALS NEAR CRITICAL CONDITIONS

ABSTRACT

Two lignites and one bituminous coal were extracted with benzene, toluene and pyridine at both sub and overcritical conditions in a specially designed experimental system which enabled easy solid-liquid separation. Extract yields increased somewhat at overcritical conditions due to more thermal decomposition. The differences between the power of the solvents were not apparent for the lignites, whereas the solubility in pyridine of the bituminous coal was very much higher than those in benzene and toluene. The amounts of oils, asphaltenes and preasphaltenes in the extracts depended on the type of coal and the solvent.     

DISSOLUTION OF COALS NEAR CRITICAL CONDITIONS

Two lignites and one bituminous coal were extracted with benzene, toluene and pyridine at both sub and overcritical conditions in a specially designed experimental system which enabled easy solid-liquid separation. Extract yields increased somewhat at overcritical conditions due to more thermal decomposition. The differences between the power of the solvents were not apparent for the lignites, whereas the solubility in pyridine of the bituminous coal was very much higher than those in benzene and toluene. The amounts of oils, asphaltenes and preasphaltenes in the extracts depended on the type of coal and the solvent.     

偶联官能化SBS改性沥青的制备及其热储存稳定性评价

选用一种新型的偶联官能化SBS,成功制备热储存稳定性良好的改性沥青,考察了SB段相对分子质量和偶联率对改性沥青性能的影响。结果表明：官能化SBS上的极性基团易与基质沥青中的极性基团相互作用,形成更有效的网状结构,从而使官能化SBS与基质沥青具有良好的相容性,改善了沥青的热储存稳定性和热性能;当SB段相对分子质量控制在6.5?104左右、偶联率在75%以上时,改性沥青性能最佳。     

热稳定添加剂对劣化环丁砜的影响及SPSS软件应用研究

考察了4种不同添加剂（2,4-二叔丁基苯酚、三乙醇胺、硫代二丙酸二月桂酯、硬脂酸铜）对劣化环丁砜热稳定性的影响。在环丁砜质量100 g、氮气流速95 mL/min、反应温度240 ℃、反应时间2 h的条件下,以SO2的释放量来评价添加剂对劣化环丁砜热稳定性的影响。结果表明：4种添加剂对劣化环丁砜热稳定性的影响由大到小的顺序为：2,4-二叔丁基苯酚>三乙醇胺>硫代二丙酸二月桂酯>硬脂酸铜;当2,4-二叔丁基苯酚添加量为劣化环丁砜质量的0.12%时,SO2的释放量为331.04 mg,抑制劣化环丁砜的热分解作用效果最好。采用SPSS软件建立了对2,4-二叔丁基苯酚用量与劣化环丁砜热分解的SO2释放量关联式,可用于实验范围内二者关系的预测。     

THE IMPORTANCE OF PYROLYSIS IN DIESEL IGNITION OF RESIDUAL FUEL OILS

ABSTRACT

Recent attempts to increase yields of distillate fuels from crude oil have resulted in a decline in the ignition quality of residual fuel oils and claims of ignition problems in large marine Diesel engines. This has revived an interest in fundamental studies of the ignition of liquid fuels and in new ways of defining and measuring ignition quality.

As part of an extensive study of the ignition of a range of residual fuels oils and during the development of novel teats of ignition quality it became obvious that thermal cracking of the fuel could play an important part in the pre-ignition chemistry. This paper reports kinetic data from simple experiments performed on the pyrolyses of residual fuel oils. Small samples and high heating rates were used to try to match the conditions inside a Blow-speed Diesel engine. This data has been used to assess the contribution that thermal cracking makes to ignition processes.

Pyrolyses were carried out on a small silica-coated platinum coil in the inlet of a gas chromatograph. Light hydrocarbon pyrolysis products were formed, and the extent and rate of cracking determined at four temperatures.

Assuming that reaction took place on a surface surrounding the oil and that a constant supply of reactants were available, pseudo zero order rate constants for the initial part of the reaction were evaluated. They showed an Arrhenius relationship with temperature giving an overall apparent activation energy of 110 kJ mol^-1. Extrapolating rate constants to temperatures expected in Diesel engines, and assuming typical droplet sizes end ignition delays, it was shown that thermal cracking of fuels was possible before ignition and that it is likely that these reactions will have a strong influence on the processes leading to ignition. It was also shown that the presence of oxygen greatly increases the rate of thermal cracking.     

高聚合度聚氯乙烯的热降解特性研究

利用热重(TG)及热重-傅立叶变换红外光谱联用仪(TG-FTIR)对高聚合度聚氯乙烯(HPVC)的热降解特性进行研究。结果表明,HPVC的热降解分为两个阶段:第一阶段以HCl的脱除为主,表观活化能较高;第二阶段则表现为碳链裂解反应。采用Jin Woo Park法研究HPVC的热降解动力学,计算热降解动力学参数。结果发现,在HPVC热降解的第一阶段,表观活化能随着失重分数的增加先降低后增加,第二阶段的表观活化能随着失重分数的增加而增加。     

柴油醇添加剂的筛选及应用

 通过对柴油醇的溶解特性和着火特性的研究，提出了由C4~C7醇+乙醚+聚合物+有机硝酸酯构成的复合添加剂。加入1%~2%复合添加剂后，柴油醇的溶解特性和十六烷值明显提高。通过发动机台架试验测定了柴油醇对发动机的冷起动性、燃烧特性和排放特性的影响。试验结果表明，加入复合添加剂后，柴油醇的冷起动性和缸内燃烧有了很大程度地改善，且着火延迟期增加很少；柴油醇的燃油消耗率有所增加而有效热效率却相应提高；烟度和NOx排放随乙醇掺合率增加而降低。     

THE IMPORTANCE OF PYROLYSIS IN DIESEL IGNITION OF RESIDUAL FUEL OILS

Recent attempts to increase yields of distillate fuels from crude oil have resulted in a decline in the ignition quality of residual fuel oils and claims of ignition problems in large marine Diesel engines. This has revived an interest in fundamental studies of the ignition of liquid fuels and in new ways of defining and measuring ignition quality.

As part of an extensive study of the ignition of a range of residual fuels oils and during the development of novel teats of ignition quality it became obvious that thermal cracking of the fuel could play an important part in the pre-ignition chemistry. This paper reports kinetic data from simple experiments performed on the pyrolyses of residual fuel oils. Small samples and high heating rates were used to try to match the conditions inside a Blow-speed Diesel engine. This data has been used to assess the contribution that thermal cracking makes to ignition processes.

Pyrolyses were carried out on a small silica-coated platinum coil in the inlet of a gas chromatograph. Light hydrocarbon pyrolysis products were formed, and the extent and rate of cracking determined at four temperatures.

Assuming that reaction took place on a surface surrounding the oil and that a constant supply of reactants were available, pseudo zero order rate constants for the initial part of the reaction were evaluated. They showed an Arrhenius relationship with temperature giving an overall apparent activation energy of 110 kJ mol^-1. Extrapolating rate constants to temperatures expected in Diesel engines, and assuming typical droplet sizes end ignition delays, it was shown that thermal cracking of fuels was possible before ignition and that it is likely that these reactions will have a strong influence on the processes leading to ignition. It was also shown that the presence of oxygen greatly increases the rate of thermal cracking.     

ASPHALTENE AND RESID PYROLYSIS: EFFECT OF REACTION ENVIRONMENT

Hondo and Maya vacuum resids and their isolated asphaltenes were pyrolyzed at 400, 425, and 450^°C (752, 797, 842^°F) for batch holding limes ranging from 20 to 180 minutes. Maltene, asphaltene, and coke product fractions were isolated by a solvent extraction sequence; gas yield was determined gravimetrically. Results were summarized in terms of a lumped reaction network. The variation of product yields, kinetics, and apparent activation energies with feedstock and asphaltene environment provided insight into asphaltene structure and thermal reaction pathways.     

THE EFFECT ON THE THERMAL EFFICIENCY OF LIME ADDED TO THE COMBUSTION CHAMBER FOR RETENTION ON SULPHUR

In order to prevent the emission of SO_x, with the flue gas, certain amount of the sulphur of the coal can be retained by adding an adequate amount of lime in the combustion chamber. In this study, two series of experiments were conducted by adding lime at the molar ratios of CaO/S = 0·5 to 2·0 using Ankara-Beypazan lignites, which have around 5 % sulphur content as received form. In one of the series lime was added directly in to the lump coal, and in the other, coal was briquetted together with lime using molasses as binder. It was observed from the experimental results that the increase in the lime ratio leads to an increase in the retained sulphur percentage while it leads to a considerable decrease in thermal efficiency. In order to retain 50 % of sulphur, it was necessary to add lime into lump coal at a CaO/S molar ratio of at least 1,1. This minimum ratio was 0·70 for briquetted coal. When lime was added at these ratios, the thermal efficiencies in the first case dropped to as low as 82 % and to 92 % in the second.