页岩油开发使美国原油加工更灵活多样

美国《世界炼油商务文摘周刊》报道由于美国页岩油产量的不断增加,使其国内炼厂原油加工更加灵活多样,原油加工量同比2011年前5个月增加了33万桶／日。其中,将近100万桶／日的原油是来自贝肯和EagleFord的页岩油,足以显示这些页岩油对美国炼厂,特别是墨西哥湾和中西部地区炼厂产生的积极影响。     

西西伯利亚油田原油的性质和组成

第十二个五年计划期间，西西伯利亚新油田应该投入开发。为制定油田开发和装备方案、准备原油集输工艺流程，及下一步原油的利用，就要搞清原油的物理化学性质和组成。     

美国页岩油产量上升原油进口量下降

美国《世界炼油商务文摘周刊》报道2008年以来,美国原油进口量一直占总消费量的2／3,而2010年这个比例下降到49．3％。进口量下降有多方面原因。其中之一是美国政府使用了新的度量标准-石油净进口量,以准确衡量国家石油进口情况。石油净进口量等于原油和成品油的进口总量扣除原油和成品油的出口总量。另一个原因是燃油消费水平下降。2010年,美国1973年后首次成为非成品油净进口国家。     

页岩油性质及脱水研究

研究了页岩油的基本性质,并分别采用瓶试法和高压电场法对页岩油脱水过程进行了实验研究,结果表明:页岩油20℃密度高达0.96 g/cm~3,含水高达9.6%(wt),含烷烃少,含烯烃和芳烃多,含有较多的氮、硫等非烃类组分和多种金属组分。页岩油的密度和黏度随温度升高逐渐降低,通过实验得到了密度-温度曲线和黏度-温度曲线。破乳剂JM-864对页岩油的破乳脱水效果最好,最佳注入量在50 mg/L~100 mg/L,最佳脱水温度在110℃~120℃。在外加400 VAC电压情况下,页岩油脱后含水可达1.8%。     

页岩油可动性分子地球化学评价方法——以济阳坳陷页岩油为例

目前,对于页岩油的可动性评价还没有规范的方法和标准,常使用热解S₁、S₁/w（TOC）及中值孔喉半径等多参数的组合并结合勘探开发实际来进行综合表征,相关地质解释理论依据相对缺乏。通过对济阳坳陷页岩油岩心样品的实验分析及研究,利用页岩油分子组成与页岩含油性及页岩油赋存空间的耦合关系,建立了表征页岩油可动性的分子地球化学评价参数模型。研究表明,当∑nC_20^-/∑nC_21⁺比值小于1时,页岩孔喉中值半径一般大于20 nm,此时,热解S₁一般大于3 mg/g,S₁/w（TOC）>100 mg/g,且随S₁、S₁/w（TOC）及页岩孔喉中值半径的增大,∑nC_20^-/∑nC_21⁺比值基本不变,反映了页岩孔喉半径达到一定级别后,喉道中大、小烃类分子扩散运动不受扩散能垒的影响,孔喉道中页岩油分子组成相对均质,页岩油可动性强;当∑nC_20^-/∑nC_21⁺比值大于1时,页岩孔喉中值半径一般小于20 nm,此时热解S₁一般小于3 mg/g,S₁/w（TOC）<100 mg/g,且随S₁、S₁/w（TOC）及页岩孔喉中值半径的减少,∑nC_20^-/∑nC_21⁺比值快速升高,反映了页岩孔喉半径小于一定级别后,大分子烃类组分在喉道中扩散运动受到扩散能垒的抑制,页岩油可动性差,易流动的主要是低分子量烃,此时页岩游离油含量也较低。济阳坳陷页岩油流动孔喉下限半径在20 nm左右。     

矿物组成对页岩油渗流机理的影响

页岩油藏岩石的矿物组成复杂,不同矿物的表面性质(如润湿性)差异较大,对页岩油的流动具有重要影响,有必要研究不同矿物孔隙内页岩油的渗流机理.文中建立了有机质、石英和方解石所构成的页岩纳米孔隙模型,以正辛烷为例,采用分子动力学模拟方法研究了页岩油的微观流动特征,为构建准确的页岩油流动方程奠定理论基础.研究表明:1)受液固之...     

页岩油:睡狮即将苏醒

在能源家族中,页岩油将扮演更加重要的角色。今后,应积极发展油页岩综合开发利用技术,制定相关扶持政策,在引进国外技术和资金的同时,应坚持"以我为主"的开发理念。     

中国页岩油资源评价方法与资源潜力探讨

鉴于我国页岩油在类型划分、评价方法、评价参数标准和资源潜力预测等方面存在较大分歧的现状,将页岩油划分为夹层页岩油、纯页岩油和原位转化页岩油三大类。根据这三大类页岩油明显不同的赋存与形成特征,分别建立了相应的容积法、基于热解烃S₁含量体积法、基于氢指数变化的生烃量法资源量计算方法模型,并确定各种方法模型的关键参数及参数下限标准,最后按照统一的参数标准评价了我国主要盆地页岩层系的三大类页岩油资源量。我国纯页岩油、夹层页岩油、原位转化页岩油地质资源量分别为145.4×10⁸, 95.1×10⁸,708.2×10⁸ t, 可采资源量分别为9.4×10⁸,7.1×10⁸,460.3×10⁸ t。评价结果表明,我国页岩油资源丰富,是推动国内原油增产稳产的重要接替领域。     

页岩油及其特征

通过与“油页岩”、“致密油”和“泥岩裂缝性油藏”等资源的对比分析,将石油勘探界的页岩油定义为以页岩为主的页岩层系中所包含的石油资源.通过分析页岩油地质特点,认为页岩油与常规石油资源有较大区别,但与页岩气在地质特征和开发方式方面有很多相似性.页岩油的“甜点”与裂缝发育程度、基质孔隙大小和地层异常压力情况关系密切.在分析鄂尔多斯盆地延长组页岩层系地质特征后认为,该区页岩油与页岩气可能存在共生现象,页岩油资源潜力巨大;中国在页岩油理论研究和勘探实践过程中应借鉴美国成功的理论模型和勘探开发经验,同时根据中美地质条件的差异性探索适合中国地质条件和经济技术水平的页岩油之路.     

不同产地页岩油的组成分析

采用柱层断分离方法,以经过处理的硅胶为吸附剂,依次用正已烷,甲苯,乙酸乙酯,甲醇为洗脱剂对内陆和海底两个不同产地的页岩油分别预分离为4个馏分。使用不同极性交联毛细管色谱柱,将各馏分分别进行色谱分离,并且用GC－MS进行了组分定性。根据各馏分的收率,结合馏分中各组分色谱峰面积归一法进行了组分的定量。在内陆页岩油中共测得质量分数大于0．2％的组分269个,其中各种烃类化合物约占79％（烷烃,烯烃和环烷烃共为52％）,其它为各种含硫,氮和氧的化合物。在海底页岩油中共测得质量分数大于0．02％的组分284个,其中各种烃类化合物约占60％（烷烃,烯烃和环烷烃共为29％）,还含有大量的含氧化合物（约占29％,主要为各种烷基酚）,其它为含硫,含氮化合物。     

油页岩干酪根热解产物特性研究

采用裂解色谱(PY-GC-MS)、电子顺磁共振波谱(EPR)和红外光谱(FTIR)等技术手段,分析了Estonia油页岩中干酪根及其热解产物的结构特性,研究了不同温度下中间产物与最终产物的关联性.结果显示:油页岩热解符合干酪根热解为中间产物热沥青,热沥青再热解为页岩油、干馏气和半焦等产物反应路径,中间产物热沥青的生成趋...     

油页岩和低阶煤干酪根热降解产物的组成及其地化意义

干酪根作为沉积岩中的主要有机物,在热作用下可裂解成烃,一般认为它是主要的成油母质。由于干酪根的不溶性和相对稳定性,所以它储存了大量可靠的有关母质类型、生源构成、沉积环境等多方面的信息。因此,对干酪根的研究,引起了许多石油勘探工作者和有机地化工作者的普遍注意。     

陆相原油、生油岩、油页岩和煤等卟啉化合物的分离鉴定和对比

本文试图采用溶剂抽提、柱层析、旋转离心薄层层析、紫外可见分光、萤光分光、液相色谱、色谱-质谱等手段,对我国胜利、冀中、辽河、江汉等油田的原油及抚顺、茂名的油页岩、煤炭等样品中的卟啉化合物进行分析鉴定和研究,找出他们之间的特性和共性,以探讨原始有机质的演化及其地球化学环境.     

CRUDE OIL BIODEGRADATION AND ENVIRONMENTAL FACTORS AT THE RIUTORT OIL SHALE MINE,SE PYRENEES

Liquid oil seeps from organic-rich source rock intervals in the Eocene Armàncies Formation in the walls of the underground Riutort oil-shale mine in the SE Pyrenees. The mine was excavated at the beginning of the last century for oil shale extraction. For this study, oil samples were recovered from fractures in the mine walls, and from pools of water on the mine floor. Some oil is present at the bottom of these pools; oil also floats on the surface of the water in association with emulsions colonized by microbial mats. The oils have undergone variable degrees of biodegradation. The physical and chemical environment in the mine was studied in order to establish the controls on biodegradation processes. The results show that the degree of biodegradation depended on factors including the location of the oil (i.e. floating on the top of the water or from the bottom of a pool), and the addition of fresh seepage oil. The biodegradation observed mainly involved the progressive removal of n-alkanes, isoprenoids and some aromatics. Biodegradation was also assessed in terms of the sulphur content and by quantitative analyses of molecular markers in the aromatic fraction. These approaches indicated that at least 50% of the oil was lost as a result of biodegradation. Isotope studies were also undertaken but isotope signatures did not provide significant data. Microbiological data were consistent with data collected from chemical analyses. Evidence for the presence of hydrocarbon-degrading bacteria were obtained from laboratory studies.     

THE REACTION OF WESTERN U.S. OIL SHALE KEROGEN WITH PHENOL

ABSTRACT

Phenol reacts with Western U.S. oil shale kerogen. The acid–catalyzed reaction gives crude products which incorporate large amounts of phenol. The toluene soluble portion of the crude products was shown by ¹H, ¹³C-NMR, FIMS, and LVHR/mass spectroscopy to consist mainly of condensed phenols. However, about 15% of the carbon in this fraction is derived from kerogen fragments. These results contrast markedly with those found for other systems reacting under similar conditions. To further explore the scope of this reaction, model compounds were allowed to react with acidified phenol. Hydrocarbons were unreactive. Certain aryl ethers and substituted phenols were very reactive. Mineral matter was also found to catalyze the reaction of phenol with the toluenesu l fonic acid catalyst. These data indicate that substituted phenols and/or aryl ethers are probably important cross-linking centers for kerogen. Long straight chain aliphatic groups appear to also be present in kerogen.     

THE REACTION OF WESTERN U.S. OIL SHALE KEROGEN WITH PHENOL

Phenol reacts with Western U.S. oil shale kerogen. The acid-catalyzed reaction gives crude products which incorporate large amounts of phenol. The toluene soluble portion of the crude products was shown by ¹H, ¹³C-NMR, FIMS, and LVHR/mass spectroscopy to consist mainly of condensed phenols. However, about 15% of the carbon in this fraction is derived from kerogen fragments. These results contrast markedly with those found for other systems reacting under similar conditions. To further explore the scope of this reaction, model compounds were allowed to react with acidified phenol. Hydrocarbons were unreactive. Certain aryl ethers and substituted phenols were very reactive. Mineral matter was also found to catalyze the reaction of phenol with the toluenesu l fonic acid catalyst. These data indicate that substituted phenols and/or aryl ethers are probably important cross-linking centers for kerogen. Long straight chain aliphatic groups appear to also be present in kerogen.     

原油蜡含量测定方法比较

 对四种测定原油蜡含量标准方法进行了比较,发现得到的结果差别明显,并具有一定的规律性。四种方法测定原油蜡含量的数值从大到小顺序为UOP 46> SY/T 0537 >SY/T 7550>ГОСТ 11851。产生这些差别的原因主要是四种标准方法的脱蜡条件及脱蜡溶剂的组成都有一些不同,每种脱蜡溶剂在相应脱蜡条件下对蜡的溶解性不同造成的。对所得蜡样品组成分析结果表明,蜡的溶解性差异主要来自于小于C25的正构烷烃和所有非正构烷烃。     

COMPARISON OF POROSITY-DEPTH RELATIONSHIPS OF SHALE AND SANDSTONE*

The rate of shale compaction or porosity reduction decreases with increase in burial or compaction. This may be caused by decreasing shale permeability and increasing water viscosity, thus decreasing rate of fluid expulsion with increasing compiction. For a given increase in overburden pressure, the pressure or stress applied to a given grain-to-grain contact area decreases with burial becaused the contact area increases with compaction and concomitant grain deformation. This may also cause the reduced rate of compaction with increase in burial. The above abservations may suggest that the shale compaction is primarily controlled by physical forces of sedimentary rocks. On the contrary, the rate of sandstone porosity reduction is known to be relatively constant throughout the burial diagenetic history in many regions provided ther was no significant secondary porosity developed by leaching and fracturing. For a given increase in overburden pressure, the grain-to-grain contact area. Yet, rate of porosity reduction for the sandstones is realtively constant, whether they are at a shallow or deep burial depth. This suggests that, for the sandstones, the physical forces have been of secondary importance in reducing the porosity. Chemical and mineralogical agents are believed to have been more significant in sandstones. Numerous regional petrographic studies confiirm the importance of diagenetic cements.     

THE COLLOIDAL STABILITY OF CRUDE OILS AND CRUDE OIL RESIDUES

ABSTRACT

A crude oil and three residues of the crude oil processing were investigated by determination of flocculation points of both the product solutions and the original products. Diverse analytical methods were used for characterizing products and their fractions. The evaluation of results was performed by the theory of regular solutions and its extension by Hansen. It was found, that the colloidal disperse phase shows a behaviour similar to that of polymer solutions. The conditions of the destabilization of the colloids can be defined by the critical Flory-Huggins interaction parameter. The solvation and the low soluble part of the asphaltenes have the greatest influence on the colloidal stability. The lowest stability is found for the visbreaking residue. The influence of the crude oil distillation on the colloidal stability is not significant.     

THE COLLOIDAL STABILITY OF CRUDE OILS AND CRUDE OIL RESIDUES

A crude oil and three residues of the crude oil processing were investigated by determination of flocculation points of both the product solutions and the original products. Diverse analytical methods were used for characterizing products and their fractions. The evaluation of results was performed by the theory of regular solutions and its extension by Hansen. It was found, that the colloidal disperse phase shows a behaviour similar to that of polymer solutions. The conditions of the destabilization of the colloids can be defined by the critical Flory-Huggins interaction parameter. The solvation and the low soluble part of the asphaltenes have the greatest influence on the colloidal stability. The lowest stability is found for the visbreaking residue. The influence of the crude oil distillation on the colloidal stability is not significant.