重油沥青质质量分数快速测定方法

采用热溶剂过滤法与抽提回流法（SH/T 0509—2010）,分别以正庚烷和甲苯为萃取剂,对5种重油的甲苯和正庚烷不溶物的元素组成质量分数及形貌进行了分析与表征,并且对比了重油沥青质质量分数的测定数据。结果表明:在萃取剂/原料油（体积/质量比）为30∶1（以甲苯为萃取剂）或100∶1（以正庚烷为萃取剂）,滤膜孔径为0.45 μm,萃取温度为80 ℃的最佳条件下,热溶剂过滤法与抽提回流法所得沥青质质量分数相当。热溶剂过滤法具有分析速度快、适用性强、准确度高的特点,实现了甲苯和正庚烷不溶物质量分数同步测定的目标。     

The Structural Characterization of Saturate,Aromatic, Resin,and Asphaltene Fractions of Batiraman Crude Oil

Abstract

The structural characterization of fractions of Batiraman crude oil, which is the heavy crude oil from a field in the southeastern part of Turkey, was investigated. Batiraman crude oil and its saturate, aromatic, resin, and asphaltene (SARA) fractions were seperated. Treatment of crude oil with n-heptane provided the separation of asphaltene. Maltene was collected by evaporating the n-heptane from the filtrate. Then, maltene was separeted into saturates, aromatics, and resins by SARA technique. Maltene was separated into saturate, aromatic, and resin fractions using column chromatography. SARA fractions were quantified on a weight percent basis. Fractions of Batiraman crude oil were characterized by elemental analysis, proton nuclear magnetic resonance (¹H NMR) analysis, electrospray ionization mass spectrometry (ESI-MS), and Fourier transform infrared (FTIR) spectroscopy techniques.     

南海原油胶质、沥青质结构表征及原油降黏研究

南海原油储量丰富,其开发利用具有重要的经济价值和战略意义。从南海原油中分离出胶质和正庚烷沥青质并对其进行表征,合成了含氮长链聚合物型降黏剂,同时考察了合成降黏剂对南海原油的降黏效果。结果表明：南海原油属高胶质、高沥青质原油,胶质和沥青质容易形成缔合结构是其黏度较高的主要原因;胶质和沥青质分子具有由烷基链连接起来的含有侧链的芳香片结构,且含有形成氢键的极性基团,胶质和沥青质的平均相对分子质量分别为760和1 129;构建的南海原油胶质和沥青质平均分子结构式参数与表征结果吻合;添加1 000 μg/g降黏剂的南海原油在15 ℃和40 ℃下的降黏率分别为44.2%和40.2%,屈服应力值从1 070 Pa降至563 Pa,降黏效果显著。     

水包稠油乳状液中孤岛稠油组分间相互作用初探

 研究了孤岛稠油脱沥青质油、胶质、沥青质及胶质与沥青质混合物对水包稠油乳状液界面性质的影响。结果表明，具有高芳碳率、低烷基碳率、高芳香环缩合程度的沥青质组分界面活性较高。在水包稠油乳状液形成过程中，芳香分的存在有利于以稠合芳香环系为核心的胶质粒子的溶解，促进胶质单元结构在油滴表面的吸附，使脱沥青质油的界面活性高于胶质。胶质对沥青质有很好的分散作用，使沥青质在油相中溶解度增加，沥青质分子以较小的缔合体或以自由分子状态存在，沥青质分子中所有极性基团较易到达表面上，使油水界面张力降低。稠油组分与阴离子乳化剂LAS存在正的协同作用，与非离子乳化剂OP-10存在负的协同作用。稠油各组分共同与乳化剂作用形成稳定的水包稠油乳状液。     

Study of asphaltene dispersion and removal for high-asphaltene oil wells

Many wellbores are blocked by asphaltene deposits,which lead to production problems in the oilfield development process.In this paper,methods such as elemental analysis,and solvent extraction are adopted for the study of wellbore blockages.The content of organic matter in blockages is higher than 96% and asphaltene is the main component of the organic matter with n-heptane asphaltene content of 38%.Based on the above analyses,an agent for asphaltene dispersion and removal(named as SDJ) was developed.The performance of the SDJ agent was evaluated,and it was found that the dissolution rate of asphaltene can reach 2.9 mg.mL-1.min-1 at 60 oC.SDJ agent(1wt%) was added to crude oil with a colloid instability index greater than 0.9 can effectively inhibit asphaltene deposition in the wellbore.By the viscosity method,the dissolution amount of SDJ agent was calculated,and it was found that when the viscosity of the system is around 2,000 mPa.s(the common viscosity of crude oil),the amount of SDJ agent added to the blockage was at least 96 g per 100 g blockages.Therefore,SDJ agent has promising application for dispersion and removal of asphaltene deposition in high-asphaltene wells.     

Deposition and flocculation of asphaltenes from crude oils

A crude oil has four main constituents: saturates, aromatics, resins, and asphaltenes. The asphaltenes in crude oil are the most complex and heavy organic compounds. The classic definition of asphaltenes is based on the solution properties of petroleum residuum in various solvents. Asphaltenes are a solubility range that is soluble in light aromatics such as benzene and toluene, but are insoluble in lighter paraffins. The particular paraffins, such as n-pentane and n-heptane, are used to precipitate asphaltenes from crude oil. Deposition of asphaltenes in petroleum crude and heavy oil can cause a number of severe problems. The precipitation of asphaltene aggregates can cause such severe problems as reservoir plugging and wettability reversal. Asphaltenes can precipitate on metal surface. Cleaning the precipitation site as well as possible appears to slow reprecipitation. To prevent deposition inside the reservoir, it is necessary to estimate the amount of deposition due to various factors. The processes can be changed to minimize the asphaltene flocculation, and chemical applications can be used effectively to control depositions when process changes are not cost effective. Asphaltene flocculation can be controlled through better knowledge of the mechanisms that cause its flocculation in the first place. The processes can be controlled to minimize the asphaltene flocculation, and chemical applications can be used effectively to control depositions when process changes are not cost effective.     

原油沥青质沉积抑制及解堵技术研究进展

世界范围内原油沥青质沉积问题多有发生,对原油开采及后处理带来极大困难,研究沥青质沉积抑制技术和解堵技术具有非常重要的意义。综述了油井沥青质沉积抑制技术,包括调整生产参数和添加化学抑制剂,如天然脂肪酸类有机物、含苯环的表面活性物质、植物油类或油品加工产物、离子液体、金属氧化物纳米粒子。介绍了沥青质沉积解堵技术,包括机械法、化学法、热力法、生物法、外力场、复合解堵法等。对沥青质沉积抑制及解堵技术的未来发展趋势进行了分析,需提前对油井或管道做好评估、分析、预测,深入研究沉积抑制及解堵机理,明确不同技术的适应性,加强复合解堵技术的研究与应用。     

超临界CO2处理对长庆原油添加降凝剂效果的影响

利用超临界CO2(scCO2)与原油混相处理装置,模拟地层条件对长庆原油进行超临界CO2混相处理,通过对处理前后油样的四组分(SARA)、沥青质稳定性、蜡析出曲线、凝点、流变性分析及微观显微观察,从沥青质缔合状态与蜡结晶层面分析了超临界CO2处理对乙烯 醋酸乙烯共聚物(EVA)降凝剂添加到长庆原油作用效果的影响。结果表明,超临界CO2处理加剂原油相比未处理加剂原油具有更好的低温流动性能。超临界CO2处理会增加未加剂原油体系极性,增强沥青质缔合程度,使低温下蜡晶形貌更细小,恶化原油低温流动性,而超临界CO2处理后添加EVA降凝剂却使得蜡晶形貌向更加紧密的团簇转化。由于超临界CO2处理有利于EVA降凝剂进一步改善蜡晶形貌,故超临界CO2处理可以促进EVA降凝剂对长庆原油低温流动性的改善效果。     

ASPHALTENE PRECIPITATION AND SOLVENT PROPERTIES OF CRUDE OILS

Improved prediction of the onset of asphaltene precipitation may be achieved using refractive index (RI) to characterize crude oils and their mixtures with precipitants and solvents. Experimental measurements of RI for mixtures of several crude oils with the precipitant n-heptane, are reported at ambient conditions. Theoretical developments are described that will permit extension of these observations to reservoir conditions

Measurements of RJ at the onset of precipitation have shown that the onset occurs at a characteristic RI for each oil/ precipitant combination, supporting the premise that precipitation is dominated by London dispersion interactions and thus, that RI can be used to predict the onset of precipitation. Reports in the literature showing that the onset of precipitation occurs at constant solvent-to-precipitant ratios provide additional confirmation

The theory is developed on the assumption that London dispersion forces dominate aggregation and precipitation of asphaltenes. The interaction energy of asphaltene molecules or aggregates in a medium of oil can be expressed as a function of the difference between the RI of asphaltene and oil. The RI of live crude oil during pressure depletion can be calculated from the RI of the stock tank oil, the molar refraction of the separator gas, the formation volume factor B_o and the solution gas/ oil ratio R_s     

Study of asphaltene deposition from Tahe crude oil

Borehole blockage caused by asphaltene deposition is a problem in crude oil production in the Tahe Oilfield, Xinjiang, China. This study has investigated the influences of crude oil compositions, temperature and pressure on asphaltene deposition. The asphaltene deposition trend of crude oil was studied by saturates, aromatics, resins and asphaltenes (SARA) method, and the turbidity method was applied for the first time to determine the onset of asphaltene flocculation. The results showed that the asphaltene deposition trend of crude oil by the turbidity method was in accordance with that by the SARA method. The asphaltene solubility in crude oil decreased with decreasing temperature and the amount of asphaltene deposits of T739 crude oil (from well T739, Tahe Oilfield) had a maximum value at 60 o C. From the PVT results, the bubble point pressure of TH10403CX crude oil (from well TH10403CX, Tahe Oilfield) at different temperatures can be obtained and the depth at which the maximum asphaltene flocculation would occur in boreholes can be calculated. The crude oil PVT results showed that at 50 , 90 and 130 o C, the bubble point pressure of TH10403CX crude oil was 25.2, 26.4 and 27.0 MPa, respectively. The depth of injecting asphaltene deposition inhibitors for TH10403CX was determined to be 2,700 m.     

ASPHALTENE PRECIPITATION AND SOLVENT PROPERTIES OF CRUDE OILS

ABSTRACT

Improved prediction of the onset of asphaltene precipitation may be achieved using refractive index (RI) to characterize crude oils and their mixtures with precipitants and solvents. Experimental measurements of RI for mixtures of several crude oils with the precipitant n-heptane, are reported at ambient conditions. Theoretical developments are described that will permit extension of these observations to reservoir conditions

Measurements of RJ at the onset of precipitation have shown that the onset occurs at a characteristic RI for each oil/ precipitant combination, supporting the premise that precipitation is dominated by London dispersion interactions and thus, that RI can be used to predict the onset of precipitation. Reports in the literature showing that the onset of precipitation occurs at constant solvent-to-precipitant ratios provide additional confirmation

The theory is developed on the assumption that London dispersion forces dominate aggregation and precipitation of asphaltenes. The interaction energy of asphaltene molecules or aggregates in a medium of oil can be expressed as a function of the difference between the RI of asphaltene and oil. The RI of live crude oil during pressure depletion can be calculated from the RI of the stock tank oil, the molar refraction of the separator gas, the formation volume factor B_o and the solution gas/ oil ratio R_s     

Investigation of asphaltene deposition under dynamic flow conditions

Asphaltene deposition is one of the most serious problems, which usually occurs in oil wells, petroleum production, oil processing, and transportation facilities. Deposition of heavy organic components, especially asphaltene, can lead to wellbore blockage and impacts well economics due to reduction in oil production. Therefore, it is necessary to pay more attention to finding some solution to overcome this problem. In this study, a pipe-loop apparatus for investigation of oil stability was employed to measure deposition thickness using a thermal method. The effects of many factors such as oil type, oil temperature, oil velocity, inhibitors, and solvents on asphaltene deposition were investigated. The results showed that the deposition increased with the increasing value of the colloidal instability index. Besides, the deposition thickness increased with the decreasing velocity of oil, but did not change with oil temperature. In addition, n-heptane could result in more deposition; however, toluene had no effect on the deposition. Branched dodecyl benzene sulfonic acid (Branched DBSA) and Linear DBSA as inhibitors decreased the rate of asphaltene deposition.     

Determining the Particle Size of Asphaltenes

Abstract

Study of heavy organics and their behavior is of great importance while occurrence of their deposition in production and processing of hydrocarbon fluids. The physical properties of heavy organics, especially asphaltenes, have been a subject of controversy for several years. The aim of the present work is to determine and measure particle size of asphaltenes. Several mixtures of crude oil and n-heptane were prepared with various dilution ratios (R_v ). Two different techniques were employed to determine and measure the particle size of asphaltenes. The first was utilizing an OLYMPUS BX60, a polarizing microscope with an appropriate magnification, and the second was using high-resolution scanning electron microscopy (SEM) and X-ray diffraction techniques. The results revealed that the size of asphaltene particles is in the range of 1–4 μm for each mixture, regardless of its n-heptane content. Although the quantity of deposited asphaltene was increased by increasing the concentration of n-heptane in mixture, the particle size of asphaltene was independent of the n-heptane concentration.     

塔河常压渣油中不同沥青质的组成与结构研究

以塔河常压渣油为原料,正戊烷、正己烷和正庚烷为溶剂,分离制得3个沥青质试样C5-As,C6-As,C7-As,采用SEM,XRD,FT-IR,TG-DTG等方法,分析表征了其表面形态、晶体结构、官能团结构和热解性能等。结果表明：随着溶剂碳链的增加,C5-As,C6-As,C7-As试样的收率逐渐减小,其值分别为33.57 %,26.98 %,21.12 %; 3个试样依次表面逐渐粗糙,粒径递减;芳香片层数和芳构化程度增加;芳环取代度降低,缩合度增大;热稳定性增强,残炭增加。     

Prediction of asphaltene deposition during turbulent flow using heat transfer approach

In this study, asphaltene deposition from crude oil has been studied experimentally using a test loop and prediction using theoretical study under turbulent flow (Reynolds numbers below 5000). The effects of many parameters such as oil velocity, surface temperature and concentration of flocculated asphaltene on the asphaltene deposition were investigated. The results showed that asphaltene deposition thickness increases with increasing both surface temperature and concentration of flocculated asphaltene and decreasing oil velocity. Thermal approach was used to describe the mechanisms involved in this process and the results of data fitting showed that there are good agreements between the results of the proposed model and the measured asphaltene deposition rates.     

工业装置渣油加氢失活催化剂上的金属赋存状态研究

以工业固定床渣油加氢失活催化剂（失活剂）为研究对象,依次采用正庚烷、甲苯对其进行索氏抽提,通过对失活催化剂上金属含量、形态及分布进行分析表征,发现金属沉积量沿着物流方向呈现降低趋势。通过Raman光谱、XPS分析表征发现,渣油加氢失活剂表面沥青质类物质含量很低。渣油加氢处理催化剂的活性相主要有3种：MoS2相、NiMoS相或CoMoS相。沉积的焦炭和金属使得催化剂暴露在外表面的活性相数量非常少。     

Analyzing electrical field effect on asphaltene deposition

Asphaltenes are the heaviest and most complicated fraction in a crude oil sample and consist of condensed polynuclear aromatics, small amounts of heteroatoms (e.g., S, N, and O), and some traces of metal elements (e.g., nickel and vanadium). The main mechanisms of asphaltene deposition are precipitation (formation of asphaltene solids out of liquid phase), aggregation (formation of larger asphaltene particles), and deposition (adsorption and adhesion onto the surface). Asphaltene deposition is a major unresolved flow assurance problem in the petroleum industry, which may occur anywhere in the production system consists of reservoir, wellbore, through flowing and the separator. Asphaltene moieties in crude oil are found to carry residual surface electric charge, so by exerting an electrical field in a specific length of pipe, asphaltenes will deposit and we will have no blockage problem. Determining asphaltene electric charge is an important issue that will be done by static experiment, and then effect of electrical field on asphaltene deposition in dynamic state should be investigated. This paper discusses electric field effect on asphaltene deposition and represents a way to deposit asphaltene moieties in specific location.     

黏土稳定剂和稠油降黏剂对稠油乳状液破乳性能的影响

为研究三次采油过程中黏土稳定剂和稠油降黏剂对破乳的影响机理,采用界面膨胀流变仪考察了阳离子型黏土稳定剂NT-1A、阴离子和非离子复配型稠油降黏剂JN-1A对滨南原油及四组分破乳体系界面膜强度的影响,应用原子力显微镜观察了NT-1A、JN-1A对沥青质聚集结构和形貌的影响。结果表明:原油中沥青质有较高的扩张模量;NT-1A通过静电吸引作用促进沥青质分子交联聚集体的形成,使聚集体粒径由489 nm增至665nm,导致界面膜强度增强,原油界面扩张模量由3.23 m N/m增至5.93 m N/m,脱水率由77.27%降至7.80%;JN-1A在油水界面上的吸附能力较强,部分顶替原油中的活性组分,抑制沥青质分子在油水界面上的聚集,聚集体粒径由489 nm降至215 nm,导致界面膜强度降低,原油界面扩张模量由3.23 m N/m降至1.68 m N/m,脱水率由77.27%增至87.50%。NT-1A、JN-1A主要通过改变原油中的活性组分沥青质的交联强度,影响界面扩张模量,从而影响稠油乳状液的破乳效果。     

三元复合驱和聚合物驱采出原油组成和破乳脱水的关系

 进行了三元复合驱采出液和聚合物驱采出液与水驱采出液的对比破乳脱水实验及模拟采出液的破乳脱水实验, 考察了三元复合驱和聚合物驱采出原油与水驱采出原油组成的差异, 以及沥青质和胶质对破乳脱水效果的影响. 结果表明, 与水驱相比, 由于原油各组分与岩石表面相互作用力的差异及不同驱替液的驱替能力的差异, 三元复合驱和聚合物驱采出原油中的沥青质、胶质和芳烃含量增加. 原油中的沥青质和胶质含量的增加, 导致采出液的油、水相分离更困难, 因为沥青质和胶质是原油中对油-水界面膜强度贡献较大的组分, 其进入油-水界面使界面膜强度较大. 沥青质形成的界面膜的强度大于胶质形成的界面膜, 因此沥青质对油、水分离的影响大于胶质.     

塔里木盆地塔河油田奥陶系原油及族组分碳同位素倒转成因分析

深入剖析塔河油田奥陶系原油与族组成的碳同位素倒转机理对于成藏演化认识和油气勘探均具有重要意义。对93件奥陶系原油及族组分在平面上与深度上的碳同位素变化特征分析表明：倒转程度在平面上由东向西逐渐加深,具有较好的规律性,艾丁地区、塔河主体区、托普台地区△δ¹³C_{沥青质-非烃}值分别为-0.73‰、-0.63‰、-0.58‰,在塔河9区及周边地区与南部盐下地区为正值。艾丁地区和塔河主体区的部分井原油δ¹³C_饱和烃与δ¹³C_全油发生了倒转;δ¹³C_沥青质与其他组分碳同位素及δ¹³C_全油在塔河油田不同区域发生了不同程度的倒转;而在深度上倒转分布与原油的埋藏深度缺乏相关性,由埋藏深度引起的热力作用不是造成塔河油田奥陶系原油族组分中沥青质碳同位素与其他组分碳同位素倒转的主要原因。结合原油族组分含量、饱和烃色谱总离子图,综合分析认为原油及族组分碳同位素倒转与前期成藏之后地层抬升引起的生物降解和油气的多期次充注有关,前期充注的原油中烃类组分多被微生物降解,而沥青质不易被降解得以保留,由于成熟度低,碳同位素值较低;而后期充注的高—过成熟度油中沥青质含量很低,以其他组分尤其是饱和烃为主,由于成熟度高,碳同位素值较高,甚至大于早期充注油的沥青质碳同位素值,使混合油中出现沥青质碳同位素与其他组分碳同位素倒转的现象。因此,塔河油田奥陶系原油成藏过程及其成藏之后的次生变化是碳同位素倒转的主要原因。