TLC-FID Calibration and Accurate Weight Determination of SARA Fractions in Heavy Crude Oil

Abstract

The authors specifically aimed to separate and characterize clean saturates, aromatics, resins, and asphaltenes (SARA) fractions and develop standards for accurate quantification purposes. A standard method ASTM D4124-86 was employed for the SARA separation of an Athabasca crude oil. These four recovered fractions were analyzed by using an Iatroscan thin-layer chromatograph with flame ionization detection (TLC-FID). The Iatroscan response to the complete burnoff of known sample weights of each fraction deposited on chromarods via known volumes of standard solutions was determined and area count versus sample weight calibration graphs subsequently obtained. From the established weight versus peak area calibration curves for each pure separated SARA fraction their accurate quantitative percentage in an Athabasca heavy crude oil was determined.     

TLC/FID分析原油SARA组成方法研究

以渤海原油为研究对象,建立原油棒状薄层色谱／氢火焰离子化检测器（TLC／FID）族组分分析方法,对原油的四个族组分（饱和烃、芳烃、胶质、沥青,SARA）进行了分析。并对其影响因素展开次数、点样量、展开剂的干燥方式进行了优化,在优化所得条件下,方法的精密度RSD值为3．54％,方法重现性RSD值为3．23％。与文献报道方法相比,本文建立的方法,可将原油中的胶质和沥青两个组分分开,更能全面反应原油的族组成成分,具有分析速度快、有机溶剂用量少、操作简单等特点。最后将建立的方法应用到不同来源的原油中,结果令人满意。     

注水调剖技术提高文明寨油田采收率

该文根据文明寨油田的油藏特点，阐述了影响其水驱采收率的层内、层间因素，并对调剖技术在改善该油田吸水剖面结构、提高驱油效率及提高复杂断块油田最终采收率等方面的应用效果作了扼要论述。     

The low temperature oxidation characteristics of SARA fractions in air flooding process

The Low Temperature Oxidation (LTO) characteristics of SARA fractions isolated from light crude oil were studied applying the static oxidation experiments. The results show that the LTO reaction of SARA fractions can occur when temperature is above 50°. Under reservoir conditions, the oxidation activities of the SARA fractions were resin > aromatics > saturate. The theoretical LTO reaction rate of crude oil calculated based on the SARA oxidation characteristics is in good agreement with the measured value. Therefore, it is an effective method to reveal the LTO mechanism of crude oil by studying the LTO mechanism of SARA fractions.     

Enhanced oil recovery by nonionic surfactants considering micellization, surface, and foaming properties

Surfactants for enhanced oil recovery are important to study due to their special characteristics like foam generation, lowering interfacial tension between oleic and aqueous phases, and wettability alteration of reservoir rock surfaces. Foam is a good mobility control agent in enhanced oil recovery for improving the mobility ratio. In the present work, the foaming behavior of three nonionic ethoxylated surfactants, namely Tergitol 15-S-7, Tergitol 15-S-9, and Tergitol 15-S-12, was studied experimentally. Among the surfactants, Tergitol 15-S-12 shows the highest foamability. The effect of NaCl concentration and synthetic seawater on foaming behavior of the surfactants was investigated by the test-tube shaking method. The critical micelle concentrations of aqueous solutions of the different nonionic surfactants were measured at 300 K. It was found that the critical micelle concentrations of all surfactants also increased with increasing ethylene oxide number. Dynamic light scattering experiments were performed to investigate the micelle sizes of the surfactants at their respective critical micelle concentrations. Core flooding experiments were carried out in sand packs using the surfactant solutions. It was found that 22% additional oil was recovered in the case of all the surfactants over secondary water flooding. Tergitol 15-S-12 exhibited the maximum additional oil recovery which is more than 26% after water injection.     

The catalytic deacidification of acidic crude oil using Cu-doped alkaline earth metal oxide catalysts

Naphthenic acids (NAs) tend to cause operational problems that can lead to the deactivation of catalysts. To overcome the problem, catalytic deacidification was introduced utilizing an ammonia solution in ethylene glycol with the aids of alkaline earth metal catalyst with alumina as a support. The initial total acid number observed for NAs in n-dodecane was 4.21 mg KOH/g. In total, 1,000 mg/L of 0.4% NH₃-EG were used as the acid removal agent. Calcium, barium, and magnesium catalysts were tested in this study. The results showed Cu/Ca/Al₂O₃ was found to be the best catalyst that could be used to enhance the reaction.     

炼制含硫原油对硫黄回收装置的影响

针对石化企业炼制含硫原油后对炼油装置工艺、设备和安全造成的影响,以中国石油化工股份有限公司洛阳分公司硫黄回收装置为例,提出了合理调节炼制原油质量,混炼或掺炼劣质含硫原油,并根据硫黄回收装置的处理能力有效地控制上游装置的炼油负荷;加强巡检,密切关注鼓风机的输出电流,定时对鼓风机电机的震动情况进行测定和记录,根据变化趋势及时维护;对装置易腐蚀部位采取材质升级和加强监测力度;完善安全管理体制、提高个人安全意识等措施。     

抗垢碱提高稠油采收率机理研究

针对胜利油田夏八区块稠油油藏地层水钙镁离子浓度高,使用常规碱剂如氢氧化钠和碳酸钠等 进行驱油均会产生结垢问题,开展了具有抗垢作用的驱油用碱研究。 选用具有良好耐垢性能的偏硼酸钠 （NaBO2）进行了室内研究,并使用填砂管驱替实验评价了其驱油效果。 结果表明：虽然 NaBO2溶液降低油 水界面张力的效果不好,但其驱油效果较好。 驱替过程中,在较高的碱溶液浓度下出现了大的压差响应, 且提高采收率的幅度随着碱溶液浓度的增加而增大。 NaBO2溶液提高稠油采收率的微观机理为：碱溶液 易侵入原油中并形成分散液滴,这些液滴随即转变为 W/O 型乳状液,封堵高渗流通道,抑制黏性指进,从 而提高波及系数。     

多层砂砾岩油藏注烟道气提高采收率技术

通过在水驱多层砂砾岩油藏中注入火驱烟道气,可实现老油田提高采收率及节能环保的双目标。并联长岩心室内驱油实验结果表明,水驱后注烟道气可有效提高油藏采收率,通过气水交替注入控制气体流度能得到更好的开发效果。在室内实验的基础上,针对A油藏开展了现场试注,进一步评估注气的可行性。根据试注动态分析及数值模拟,认为注烟道气能起到明显增油效果,但多层砂砾岩油藏连续注气方式下注入气易沿高渗、薄层窜流,导致气体早期突破。油藏规模注烟道气的注采参数优化结果表明,采取分层注烟道气、水气交替注入、水气比1∶1、交替周期7 d的效果最好。目前,A油藏投注了1个分层注气井组,取得较好的增油效果。该研究成果可以为同类油藏开发提供一定借鉴。     

Enhanced heavy oil recovery and performance by application of catalytic in-situ combustion

Combustion tube experiments were carried out under various conditions to investigate the performance of catalytic in-situ combustion for recovering heavy oil. Compared with baseline experiment, the catalytic combustion exhibited better performance. Fractional oxygen gas in effluent gases was reduced by 2.9%, while fractional carbon dioxide and carbon monoxide was increased by 1.0% and 0.6%, respectively. Oxygen utilization efficiency was increased by 2.1% and apparent H/C atom ratio was lowered by 0.9%. The combustion performance was obtained under optimum experimental condition of air injection rate of 2.9?mL/min, preheated temperature of 190?°C, and grain-size gradation 2.     

水力喷射泵用于稠油热采的几个问题

用水力喷射泵开采含砂稠油，由于泵结构简单、且无运动件，解决了泵的砂卡问题。在设计喷射泵时，考虑了两个问题：一是原油粘度随油层温度的下降而增加，泵效又随原油粘度的增加而降低，为此对注蒸汽后油层温度的变化作了定性分析后，给出了可供拟合油层温度随时间变化关系曲线的温度－时间关系式。二是为方便注蒸汽，设计了一种特殊结构的底阀，可不起出底阀直接由抽转注。     

用于三次采油的新型弱碱表面活性剂

以α-烯烃为初始原料,经过烷基化及磺化、中和,研制出了组分相对单一、结构合理的新型弱碱烷基苯磺酸盐表面活性剂.室内评价结果表明,这种表面活性剂具有良好的界面活性,配制的复合体系在较宽的表面活性剂浓度和碱浓度范围可与原油形成10^-3mN/m数量级的超低界面张力.同时,该表面活性剂对大庆油田不同区块、不同油层的油水条件有很强的适应性.另外,由于表面活性剂组成较为单一,可大大降低表面活性剂在地层中因吸附滞留而产生的色谱分离效应.室内天然岩心驱油实验表明,三元复合体系平均驱油效率可比水驱提高约20%.小井距三元复合驱矿场试验结果表明,三元复合驱比水驱提高采收率24.66%.这种表面活性剂为三元复合驱技术在大庆油田的工业化推广,特别是在二类油层的应用奠定了基础.     

地下水封石洞原油库油气回收装置处理能力的确定

介绍了地下水封洞库的工作原理和特点,分析了国家石油储备库的运行模式,提出在水封洞库有一定承压能力和储备库进油作业不连续的条件下,油气回收的设计规模可适当缩小的理念.通过对进油操作的合理假设和油气状态的适当简化,推导出了有一定承压能力储备库油气回收规模的工程计算方法,并在国内某储备库应用.对3 000 dam3的地下水封洞库,在操作压力弹性为0.01～0.1 MPa的情况下,油气回收处理能力可减少约1/3,投资可降低约400万元.     

注气提高采收率技术进展及前景展望

在跟踪调研全球注气提高采收率技术发展及应用的基础上,总结分析了国外气驱提高采收率技术发展历程及CO₂驱、碳捕集利用与封存（CCUS）、烃气驱、顶部注气重力驱、空气驱等矿场成功应用实例和对中国发展气驱的启示。对中国以陆相沉积为主的油藏10余年CO₂驱（CCUS）、顶部注烃气驱、减氧空气驱等注气提高采收率技术领域形成的特色理论、关键技术和矿场试验进行了总结研究。参照美国注气技术发展历程,分析了中国适宜气驱的油藏类型及潜力、气源及注入方式、配套技术发展、试验类型及成效,明确了中国注气技术已处于从工业试验向工业化规模推广应用发展的关键阶段,未来5~10年有望上产至年产油（500~1000）×10⁴t,将发展成为中国继热采、化学驱后最重要的油田提高采收率技术,对中国原油稳产将起到重要保障作用。同时分析了中国注气技术发展尚面临油藏条件、试验类型和规模、气源供给、配套技术及成本、政策支持等方面的问题,从国家和各大石油公司层面给出了加快气驱关键技术攻关试验及有效规模应用的对策建议。     

聚合物驱后热化学沉淀调剖提高采收率技术研究

在探讨聚合物驱油后油层物性变化及剩余油分布特点的基础上,提出利用热化学沉淀进行油藏深部调剖提高采收率的方法。该方法的调剖原理不同于传统的调剖,主要通过缩小孔隙体积而达到降低高渗透层渗透率的目的。初步的物理模拟研究表明,选用硼酸钠溶液进行结晶沉淀,可以明显降低高渗透层的渗透率,且在10倍孔隙体积水洗后渗透率降低幅度仍可保持在55．8％～60．2％,并且“堵而不死”,实现真正意义上的调剖。在二维纵向非均质模型上的热化学沉淀调剖驱油实验表明,在聚合物驱后可继续提高采收率7．8％～9．2％,效果同于聚合物凝胶,并且具有注入粘度低、可进入残余油不连续分布的油藏深处等特点,尤其适合于温度适中的油藏。     

注气提高采收率技术进展及前景展望

在跟踪调研全球注气提高采收率技术发展及应用的基础上,总结分析了国外气驱提高采收率技术发展历程及CO₂驱、碳捕集利用与封存(CCUS)、烃气驱、顶部注气重力驱、空气驱等矿场成功应用实例和对中国发展气驱的启示。对中国以陆相沉积为主的油藏10余年CO₂驱(CCUS)、顶部注烃气驱、减氧空气驱等注气提高采收率技术领域形成的特色理论、关键技术和矿场试验进行了总结研究。参照美国注气技术发展历程,分析了中国适宜气驱的油藏类型及潜力、气源及注入方式、配套技术发展、试验类型及成效,明确了中国注气技术已处于从工业试验向工业化规模推广应用发展的关键阶段,未来5～10年有望上产至年产油(500～1 000)×10⁴t,将发展成为中国继热采、化学驱后最重要的油田提高采收率技术,对中国原油稳产将起到重要保障作用。同时分析了中国注气技术发展尚面临油藏条件、试验类型和规模、气源供给、配套技术及成本、政策支持等方面的问题,从国家和各大石油公司层面给出了加快气驱关键技术攻关试验及有效规模应用的对策建议。     

利用水平井提高带底油凝析气藏原油采收率

以英买7凝析气藏为研究对象，开展了利用水平井开采英买7凝析气藏底油的可行性研究和实践。采用水平井可以有效提高带底油凝析气藏原油的采收率；利用水平井开发井网，采用先期开采底油、适时上返采气的开发方式可以在不影响天然气采收率的前提下有效提高原油采收率。对英买7凝析气藏而言，将水平井部署在油气界面之上1m-2m处、水平段长度300m、速度控制在2．5％以下进行开发既不影响天然气采收率又可以提高原油采收率，对提高带底油凝析气藏的原油采收率具有重要的参考作用。     

原油碳源微生物自动寻的提高原油采收率机理

应用可视化实验观测方法,对3种原油碳源微生物提高原油采收率的机理进行的研究发现,原油碳源微生物有向原油定向运移并直接接触原油的“自动寻的”功能,并使原油碳源处菌群高度富集。这种自动寻的运移是原油碳源微生物提高原油采收率的基础。实验发现,在任何时候,原油碳源处的菌浓度比其他各处高出5~6个数量级。距原油碳源越远,菌浓度越低,其代谢产物浓度分布规律与菌浓度分布规律相符。微观模拟实验表明,高浓度的菌群及其大量代谢产物协同作用于原油碳源有利于剩余油启动。依据所得规律,对应用原油碳源微生物提高采收率的生产模式提出了建议。     

油藏岩石润湿性对采收率的影响

本文综述了油藏岩石润湿性对水驱油采收率影响的两种不同观点：一种认为弱水湿油藏水驱油采收率最高，另一种认为，弱水湿油藏水驱油采收率最高。本文所做理论分析表明，弱水湿油藏水驱油采收率最高较有依据。     

聚/表二元复合驱提高普通稠油水驱后残余油采收率的研究

采用椰油脂肪酸二乙醇酰胺型烷醇酰胺(6501)与部分水解聚丙烯酰胺(HPAM)组成二元复合驱体系,利用旋转滴法测定了该二元复合驱体系的耐温、抗盐、抗二价离子等性能,通过人造岩心物模实验和微观驱油实验分别评价了该体系的驱油效果。实验结果表明,0.1%(w)HPAM+0.3%(w)6501二元复合驱体系在40~80℃、矿化度1 000~13 000 mg/L、Ca~(2+)含量50~350 mg/L范围内的油水界面张力在10~(-3)~10~(-2) m N/m间保持稳定;人造岩心物模实验和微观驱油实验结果均显示,水驱后注入聚合物驱或二元复合驱时,二元复合驱体系较单独的聚合物驱可进一步提高采收率。