CHARACTERIZATION OF VARIOUS BITUMEN SAMPLES FROM TAR SANDS

We have investigated twenty three bitumen samples obtained using different separation methods such as: ultracentrifugation, Dean-Stark extraction, solvent extraction employing vigorous agitation, hot water separation and the Solvent Extraction Spherical Agglomeration technique. These samples were extracted from oil sand feedstocks of different grades, Suncor sludge pond tailings and mineral agglomerates obtained from the Solvent Extraction Spherical Agglomeration process. All of the bitumen samples were examined on a comparative basis using various analytical techniques. These included: fractionation into asphaltenes and maltenes; elemental analyses; molecular weight determination using vapour pressure osmometry and gel permeation chromatography, infrared, proton and 13C nuclear magnetic resonance spectroscopy. Proton and ¹³C n.m.r. spectroscopic data were used to determine the distribution of various types of hydrogens and carbons in the samples. These data were also used to derive various molecular parameters in order to investigate average molecular structures of different bitumen samples and some of their asphaltene fractions.     

AN EXPERIMENTAL APPROACH OF ELEMENTAL SULFUR DEPOSITION IN CARBONATE OIL RESERVOIRS

The existence of sulfur compounds in crude oils creates many problems of sulfur deposition in the vicinity of the wellbore hole, in well completion and/or production equipment, and in producing reservoir rocks. The major objectives of this experimental study are to investigate the influences of oil flow rate, initial sulfur concentration of crude oil, and reservoir rock permeability on elemental sulfur plugging in carbonate oil reservoirs. To achieve these objectives, actual crude oils were de-asphaltened to eliminate the effect of asphaltene deposition. Ten dynamic flow experiments were conducted using two actual crude oils of 0.78 and 1.67% sulfur concentrations. Viscosity of crude oils of different sulfur concentrations was measured under different conditions of temperature. The crude oils were flooded through actual carbonate cores of different permeability in the range of 2.34-28.16 millidarcy and under different flow rates of 0.5, 1.0, 1.5, and 2.0 cc/min. In-situ sulfur deposited was measured using Scanning Electron Microscopy (SEM) to provide the amount of sulfur deposited along the core samples. The results indicated that crude oil of higher sulfur concentration has higher viscosity than that of one of lower concentration. The deposition of elemental sulfur does not take place at the low rate of 0.50 cc/min, starts at 1.0 cc/min and increases as the flow rate increases up to 1.50 and 2.00 cc/min, respectively. In addition, the higher sulfur concentration of the crude oil increases the deposition of sulfur in carbonate oil reservoirs. The results also showed that permeability of carbonate reservoir rocks has a severe effect on sulfur deposition since carbonate rocks of higher permeability do not experience the problem of elemental sulfur deposition while the problem is more severe for lower permeability rocks. In addition, the depositional rate is accelerated rapidly as the rock permeability decreases. The obtained results of this study have important interest in identification of the most important factors affecting the elemental sulfur precipitation in heterogeneous carbonate oil reservoirs and robust implications in the development of reservoir simulation models.     

新疆油砂稠油制特种沥青

以新疆小西沟、风城两种油砂为原料，利用甲苯抽提制取的油砂稠油研制开发高价值的特种沥青产品。实验室的研究结果表明，小西沟油砂稠油可用作管道防腐沥青；风城油砂稠油分别与克拉玛依减压渣油和孤岛减压渣油调合后可制取油漆沥青和抛光沥青。     

油砂沥青改质产品中甲苯不溶物的表征

油砂沥青及其衍生产品中含有悬浮的甲苯不溶物如粘土和碳质固体颗粒，会导致后续加工过程中的结垢、催化剂失活和床层堵塞。笔者从油砂沥青衍生产品中分离出甲苯不溶物并进行了分析表征。研究发现，油砂沥青渣油中的甲苯不溶物主要是超细的硅铝酸盐粘土颗粒，结合了部分干酪根成分；焦化渣油和焦化瓦斯油储罐中沉积的甲苯不溶物类似焦炭；焦化瓦斯油中的甲苯不溶物主要是碳质有机物颗粒，但氮、氧含量相对丰富，并含少量矿物质和粘土颗粒，含氮的杂环化合物如吡咯类物质的存在可能是导致焦化瓦斯油中甲苯不溶物生成的主要因素。     

DEMINERALIZATION OF PETROLEUM COKES AND FLY ASH SAMPLES OBTAINED FROM THE UPGRADING OF ATHABASCA OIL SANDS BITUMEN

ABSTRACT

Ash reduction of the cokes and fly ash samples derived from the Athabasca oil sands bitumen was attempted by dissolving the mineral matter in acids. The samples used for this investigation included Syncrude fluid coking coke, Suncor delayed coking coke and the two fly ash samples obtained from the combustion of these cokes. All samples were analyzed for C,H,N,0 and S before and after acid demineralization and the analyses results compared. Further, the ash from the samples before and after acid demineralization was analyzed for silica, alumina, iron, titanium, nickel and vanadium to assess the acid leaching of these elements. CP/ MAS, ¹³C NMR spectroscopic study of the demineralized coke and fly ash samples was also attempted     

DEMINERALIZATION OF PETROLEUM COKES AND FLY ASH SAMPLES OBTAINED FROM THE UPGRADING OF ATHABASCA OIL SANDS BITUMEN

Ash reduction of the cokes and fly ash samples derived from the Athabasca oil sands bitumen was attempted by dissolving the mineral matter in acids. The samples used for this investigation included Syncrude fluid coking coke, Suncor delayed coking coke and the two fly ash samples obtained from the combustion of these cokes. All samples were analyzed for C,H,N,0 and S before and after acid demineralization and the analyses results compared. Further, the ash from the samples before and after acid demineralization was analyzed for silica, alumina, iron, titanium, nickel and vanadium to assess the acid leaching of these elements. CP/ MAS, ¹³C NMR spectroscopic study of the demineralized coke and fly ash samples was also attempted     

内蒙古油砂油减压渣油制备特种沥青的研究

以内蒙古油砂油减压渣油为原料，分别与克拉玛依减压渣油、孤岛减压渣油、辽河减压渣油和胜利减压渣油以不同比例调合，考察制备抛光沥青、油漆石油沥青等特种沥青的可行性。结果表明，油砂油减压渣油与克拉玛依减压渣油以25：75的质量比调合后，可作60号抛光沥青，以30：70质量比调合后，可作3号油漆石油沥青；油砂油减压渣油与孤岛减压渣油以 40 ： 60的质量比调合后，可做60号抛光沥青；油砂油减压渣油与辽河减压渣油、胜利减压渣油调合后，调合沥青不宜作特种沥青。     

STUDY ON THE PREPARATION OF ASPHALT WITH SPECIAL USES FROM CHINESE TAR SANDS

ABSTRACT

Tar sand heavy oil ( TSHO ) was extracted from Xinjiang Xiaoxigou and Fengcheng tar sands. The basic properties of the TSHO were investigated. It is found that the TSHOs are not suitable to produce paving asphalt. However, some asphalt products with special uses were prepared from the TSHOs. The results show that Xiaoxigou TSHO can be used to produce anticorrosion asphalt for pipeline. Fengcheng TSHO, blended with kramai vacuum residuum and Gudao vacuum residuum, can be used to produce painting and polishing asphalt. The influence of the blending asphalt's SARA compositions on their qualities was also investigated.     

STUDY ON THE PREPARATION OF ASPHALT WITH SPECIAL USES FROM CHINESE TAR SANDS

Tar sand heavy oil ( TSHO ) was extracted from Xinjiang Xiaoxigou and Fengcheng tar sands. The basic properties of the TSHO were investigated. It is found that the TSHOs are not suitable to produce paving asphalt. However, some asphalt products with special uses were prepared from the TSHOs. The results show that Xiaoxigou TSHO can be used to produce anticorrosion asphalt for pipeline. Fengcheng TSHO, blended with kramai vacuum residuum and Gudao vacuum residuum, can be used to produce painting and polishing asphalt. The influence of the blending asphalt's SARA compositions on their qualities was also investigated.     

A NOVEL TECHNIQUE OF ASPHALTENE DEPOSITION TREATMENT USING ULTRASONIC IRRADIATION

The need for better understanding of asphaltene behavior in the crude oil and treatment techniques of its deposition in porous medium has been recognized but still requires extensive research and experimental activities. The ambitious goals of this study are to investigate: (1) influences of using ultrasonic irradiation on asphaltene behavior in the UAE crude oil, with consideration of solvent and temperature effects; and (2) influences of ultrasonic irradiation characteristics such as frequency and time interval on damaged oil permeability (due to asphaltene deposition) of carbonate reservoir rocks. To achieve the above-mentioned goals, three groups of experiments using ultrasonic irradiation were carried out. In the first group, 18 identical crude oil samples of 2.47 wt% initial asphaltene content were subjected to different time intervals of ultrasonic irradiation of 0, 5, 10, 15, 25 and 30 min and under different temperatures of 25, 40 and 60°C, respectively. Oil viscosity was measured and microscopic images of the centrifugated oil samples of asphaltene clusters were obtained. In the second set of experiments, 12 identical crude oil samples with different toluene concentrations of 5, 10, and 15 vol% were subjected to four different durations of ultrasonic irradiation and under different temperatures. In the third group, seven actual carbonate core samples of damaged oil permeability due to the injection of 60 pore volumes of asphaltic crude oil were subjected to different ultrasonic time interval of 5, 10, 15, 20, and 25 min and frequencies of 10, 15 and 20 kHz, respectively. Both the oil permeability of these samples was measured and the scanning electron microscope (SEM) images were carried out before and after the ultrasonic irradiation process. The results showed that subjection of the UAE crude oil to ultrasonic irradiation decreases the size of asphaltene clusters. Consequently, this effect reduces asphaltene tendency to precipitate at 10 min or more time interval of ultrasonic irradiation. In addition, similar results were obtained with solvent effect, but with more reduction in oil viscosity. The results also indicated that the increase of ultrasonic time interval and/or frequency drastically improve(s) damaged oil permeability.     

A NOVEL TECHNIQUE OF ASPHALTENE DEPOSITION TREATMENT USING ULTRASONIC IRRADIATION

ABSTRACT

The need for better understanding of asphaltene behavior in the crude oil and treatment techniques of its deposition in porous medium has been recognized but still requires extensive research and experimental activities. The ambitious goals of this study are to investigate: (1) influences of using ultrasonic irradiation on asphaltene behavior in the UAE crude oil, with consideration of solvent and temperature effects; and (2) influences of ultrasonic irradiation characteristics such as frequency and time interval on damaged oil permeability (due to asphaltene deposition) of carbonate reservoir rocks. To achieve the above-mentioned goals, three groups of experiments using ultrasonic irradiation were carried out. In the first group, 18 identical crude oil samples of 2.47 wt% initial asphaltene content were subjected to different time intervals of ultrasonic irradiation of 0, 5, 10, 15, 25 and 30 min and under different temperatures of 25, 40 and 60°C, respectively. Oil viscosity was measured and microscopic images of the centrifugated oil samples of asphaltene clusters were obtained. In the second set of experiments, 12 identical crude oil samples with different toluene concentrations of 5, 10, and 15 vol% were subjected to four different durations of ultrasonic irradiation and under different temperatures. In the third group, seven actual carbonate core samples of damaged oil permeability due to the injection of 60 pore volumes of asphaltic crude oil were subjected to different ultrasonic time interval of 5, 10, 15, 20, and 25 min and frequencies of 10, 15 and 20 kHz, respectively. Both the oil permeability of these samples was measured and the scanning electron microscope (SEM) images were carried out before and after the ultrasonic irradiation process. The results showed that subjection of the UAE crude oil to ultrasonic irradiation decreases the size of asphaltene clusters. Consequently, this effect reduces asphaltene tendency to precipitate at 10 min or more time interval of ultrasonic irradiation. In addition, similar results were obtained with solvent effect, but with more reduction in oil viscosity. The results also indicated that the increase of ultrasonic time interval and/or frequency drastically improve(s) damaged oil permeability.     

快速溶剂萃取法提取印尼油砂沥青的工艺研究

采用快速溶剂萃取技术提取油砂沥青,通过单因素试验和正交试验得出加压溶剂萃取技术的最佳工艺参数。研究结果表明,在高压条件下,混合适量硅藻土分散剂,快速溶剂萃取法提取油砂沥青比传统索氏抽提与费舍尔试验更有优势。利用正交试验获得快速溶剂萃取法提取油砂沥青的最佳工艺参数为：压力10 MPa,土砂比(硅藻土与油砂的体积比)2∶1,萃取温度160℃,循环次数5次,溶剂选择四氢呋喃,单次静态萃取时间12 min。     

A CORRRELATION OF UNITED STATES TAR BAHD BITUMEN VISCOSITIES WITH EMR SPECTROSCOPIC PARAMETERS

ABSTRACT

Many physicochemical properties of bitumens must be known in order to mathematically model and simulate the processes used for the recovery of bitumen from tar sands. One fundamental property is the temperature dependence of viscosity. This property determines the heat transfer and flow characteristics of a bitumen through a porous media.

A method has been developed whereby the viscosity of a tar sand bitumen at any temperature can be calculated from nuclear magnetic resonance parameters. The method is semiempirical but is based upon some fundamental theoretical concepts for molecular mobility and intermolecular interactions. Using this method, the viscosities of three United States tar sand bitumens have been correlated to the weighted average spin-spin relaxation rates for the semiliquid, solidlike mobile, and solidlike rigid phases of the bitumens. The results indicate that bitumens with a high viscosity have a greater amount of solidlike rigid phase and lesser amounts of solidlike mobile and semiliquid phases than do the bitumens with low viscosity. It is also shown that the viscosity of a tar sand bitumen over a 100 degree temperature range can be determined from a single NMR experiment conducted near room temperature.     

KINETICS OF HYDRODESULFURIZATION OF HEAVY GAS OIL DERIVED FROM OIL-SANDS BITUMEN

With gradual shortage in the supply of crude oil, the importance of producing synthetic crude oil from oil sands and shale oil is increasing day by day. In the present paper, the effects of various process variables such as temperature, liquid hourly space velocity and hydrogen/heavy gas oil volumetric ratio on the removal of sulfur compounds from oil sands derived heavy gas oil has been studied. The experiments have been carried out in a micro scale trickle bed reactor over a commercial Ni-Mo catalyst. The temperature, liquid hourly space velocity and hydrogen/heavy gas oil volumetric ratio have been varied from 365 to 415°C, 0.5 to 1.9 h^-1 and 400 to 1000 ml, respectively. Under optimum reaction conditions over 96% conversion of sulfur compounds was achieved. The kinetics of the rate of sulfur removal from the oil sands derived heavy gas oil has also been discussed in this article.     

KINETICS OF HYDRODESULFURIZATION OF HEAVY GAS OIL DERIVED FROM OIL-SANDS BITUMEN

ABSTRACT

With gradual shortage in the supply of crude oil, the importance of producing synthetic crude oil from oil sands and shale oil is increasing day by day. In the present paper, the effects of various process variables such as temperature, liquid hourly space velocity and hydrogen/heavy gas oil volumetric ratio on the removal of sulfur compounds from oil sands derived heavy gas oil has been studied. The experiments have been carried out in a micro scale trickle bed reactor over a commercial Ni–Mo catalyst. The temperature, liquid hourly space velocity and hydrogen/heavy gas oil volumetric ratio have been varied from 365 to 415°C, 0.5 to 1.9 h^?1 and 400 to 1000 ml, respectively. Under optimum reaction conditions over 96% conversion of sulfur compounds was achieved. The kinetics of the rate of sulfur removal from the oil sands derived heavy gas oil has also been discussed in this article.     

内蒙古油砂油的综合评价

对内蒙古油砂油性质进行了综合评价。结果表明，该油砂油密度大（20℃密度为0．9996g／cm^3），粘度较大，水含量高（16．0％），胶质、沥青质含量高，硫质量分数为2．64％，属高硫环烷基原油。油砂油各馏分的密度、粘度均较大。根据该油砂油的特性，建议该油砂油经加工后用作低凝点柴油和润滑油的调合组分，并用于重交通道路沥青的生产。     

塔里木不同成因原油芳烃组成和分布特征

从芳烃组成上,塔里木原油可划分为塔北台地相原油、塔中局限性海湾(泻湖)相原油和湖相油、煤成油四种成因类型.塔中原油以高二苯并噻吩系列(>30%)和低菲系列(<15%)为特征,区别于塔北海相原油;煤成油则以高联苯(>20%)、二苯并呋喃系列(>5%)有别于湖相油.这些不同成因原油的烷基萘、菲异构体分布明显不同.海相油的1,2,5-/1,3,6-TMN小于0.3,而湖相油和煤成油的此比值分别大于0.3和0.6.原油的1,2,7-/1,3,7-TMN可识别源岩的地质时代.与海相油相比,陆相油尤其是煤成油的9-甲基菲占优势,与国外的研究结果不同.     

沥青质中官能团结构和氢键的红外光谱表征

利用傅里叶红外光谱表征渣油沥青质和煤焦油沥青质分子的官能团结构,并通过软件Origin 2018对沥青质红外光谱的氢键区、脂肪族碳氢伸缩振动区和C—O区的吸收峰进行分峰拟合。结果表明：两种沥青质均主要以碳、氢元素为主,二者杂原子的含量存在明显差异,但杂原子官能团的类型基本相同;渣油沥青质中的氢键主要是由苯环O—H与芳香醚键中的O原子、O—H自缔合形成的氢键,而煤焦油沥青质中的氢键主要是苯环O―H与芳香醚键中的O原子形成的氢键;与渣油沥青质相比,煤焦油沥青质的烷基侧链更短。     

GEOCHEMISTRY OF SEEP AND PRODUCED OIL SAMPLES FROM SOUTHERN CAMEROON

Crude oil samples from surface seeps in the Douala Basin (southern Cameroon) and from producing fields in the nearby Rio del Rey and Kribi‐Campo sub‐basins were analysed for bulk and molecular geochemical parameters by inductively coupled plasma – mass spectrometry (ICP‐MS), gas chromatography – mass spectrometry (GC‐MS) and isotope ratio mass spectrometry (IRMS). The aims of the study were to assess the composition of the oils, to evaluate the relationship between the seep oils and the oils from producing fields, and to highlight the significance of the data for oil exploration in the region. Chromatograms of the saturate fractions of the oils exhibit biodegradation ranging from very light (PM1 on the scale of Peters and Moldowan, 1993) in oil from the offshore Lokele field in the Rio del Rey sub‐basin, to severe (PM 6+) for seep oils from the Douala Basin. A plot of Pr/n‐C₁₇ (1.3– 5.0) versus Ph/n‐C₁₈ (0.8–2.6) for the samples further supports mild biodegradation in some samples (Lokele, Kole, Ebome), and demonstrates that the oils from the Lokele and Kole fields (Rio Del Rey sub‐basin) and from Ebome field (Kribi‐Campo sub‐basin) originated from mixed organic matter with a dominant marine contribution. The Pr/Ph ratio (1.8–2.3) for the Lokele, Kole and Ebome oil samples, and the V/(V+Ni) ratios (< 0.5) for the seep oils (Douala Basin) and the oils from the Lokele, Kole and Ebome fields, indicate derivation from source rocks deposited in oxic – dysoxic environments. The CPI (1.0–1.1) demonstrates that the Lokele and Ebome oils originated from mature source rocks, with the ratios of C₃₁ 22S/(S+R) (0.57 to 0.63) and C₃₀‐βαH/C₃₀‐αβH (0.18–0.23) for the Lokele, Kole and Moudi samples indicating early oil window maturity. Both V/(V+Ni) ratios (0.06–0.22) and δ¹³C (‐26.96 to ‐24.89 ‰) were used for correlation of the oils, with the seep oils from the Douala Basin showing the closest relationship to the oil from the Lokele field. The presence of mature Type II / III source rocks in different basins in southern Cameroon suggests significant potential for oil exploration in the region.     

印尼油砂溶剂抽提工艺条件的研究

对印尼油砂的组分、结构和粒径特征进行分析。分析结果表明，从印尼油砂中分离稠油沥青适用的方法是溶剂抽提工艺。考察了三氯乙烯、甲苯、石油醚、石脑油、含极性组分的石脑油5种溶剂对抽提效果的影响，确定较佳的抽提溶剂为含极性组分的石脑油。考察了印尼油砂溶剂抽提的工艺条件，推荐的最佳工艺参数为：溶剂与油砂的体积比1.3：1，抽提温度50～60 ℃，抽提时间15～30 min，搅拌速率100～300 r/min。在该条件下，稠油沥青一级抽提率达85%，二级抽提率达93%。