The Use of Microscopic Bitumen Froth Morphology for the Identification of Problem Oil Sand Ores

Oil sand, which is found in various deposits around the world, consists mostly of sand, surrounded by up to 18 wt% bitumen. The largest deposits known are situated in northern Alberta, Canada, where reserves of bitumen are estimated to be 1.7 trillion barrels. Bitumen is similar to heavy oil, but with much higher viscosity and density. The two main commercial oil sand operations in Alberta are surface mines and use aqueous flotation of the bitumen to separate it from the rest of the oil sand. Under optimal conditions up to 95% of the bitumen can be recovered, but occasionally ores are mined that create problems in extraction, and recovery can drop to 70% or less. This article discusses the microscopic morphologies of various bitumen and heavy oil streams and their relationship to processing problems. The results of extensive microscopic work have demonstrated that the bitumen in an oil sand ore is the phase most susceptible to oxidation and that the resulting changes manifest themselves in particular microscopic structures. The presence and type of these structures can be related to the processing behavior of oil sand ores. Morphological features found in froths from commercial operations are similar to those found in froths from laboratory-prepared samples. The morphological features found in froths of oxidized ores have been categorized and quantified for a variety of samples and are referred to as degraded bitumen structures. Experiments in which fresh oil sand ores were subjected to low-temperature oxidation showed that bitumen froth morphology changed dramatically compared to that of nonoxidized ores for identical bulk compositions and extraction water chemistries.     

Athabasca oil sands: effect of organic coated solids on bitumen recovery and quality

The Canadian oil sands deposits in northern Alberta contain about 1.3 trillion barrels of crude oil equivalent. The largest of the four major formations is found in the Athabasca region where bitumen is heterogeneously distributed throughout an unconsolidated mineral matrix. About one-tenth of the oil sands in this deposit is economically recoverable by conventional surface mining techniques.The Hot Water Extraction Process (HWEP) is used commercially to recover bitumen from surface mined oil sands ore. The viability of this process relies on the existence of a thin water film around each solid particle in the ore matrix. However, a completely water-wet mineral condition is not generally the case for oil reservoirs, including oil sands deposits. In the latter case, it has been shown that certain solid fractions are associated with significant amounts of toluene insoluble organic matter (TIOM), physically or chemically adsorbed onto particle surfaces. These fractions are generically described as ‘organic rich solids’ (ORS). In bitumen separation processes, the organic matter associated with various ORS fractions represents an impediment to optimum bitumen separation and upgrading. In this sense, these solids are considered to be ‘active’ relative to the ‘inactive’ water wetted quartz particles comprising the bulk of the oil sands ore. Preliminary results indicate that the ORS content of an ore appears to be a better predictor for ore processability than the traditional use of bitumen or fines (−44 μm) contents.Two types of ORS have received particular attention. The first is a coarser fraction, usually less than 44 μm but also occurring as particles greater than 100 μm in diameter. This material typically occurs as aggregates of smaller particles bound together by humic matter and precipitated minerals. During the bitumen separation process, these heavy aggregates carry any associated bitumen into the aqueous tailings, thus reducing overall bitumen recovery. The second important fraction comprises very thin, ultra-fine clay particles with a major dimension of <0.3 μm. These ultra-fine clays, with a surface coating of organic matter, remain with bitumen during the separation process. In bitumen upgrading, these solids may be entrained with volatile overheads and cause problems in downstream operations. This paper summarises the protocols developed to separate and characterise these intractable components from HWEP process streams and discusses their role in determining bitumen recovery and quality.     

Biodegradation and origin of oil sands in the Western Canada Sedimentary Basin

The oil sands deposits in the Western Canada Sedimentary Basin （WCSB） comprise of at least 85% of the total immobile bitumen in place in the world and are so concentrated as to be virtually the only such deposits that are economically recoverable for conversion to oil. The major deposits are in three geographic and geologic regions of Alberta： Athabasca, Cold Lake and Peace River. The bitumen reserves have oil gravities ranging from 8 to 12° API, and are hosted in the reservoirs of varying age, ranging from Devonian （Grosmont Formation） to Early Cretaceous （Mannville Group）. They were derived from light oils in the southern Alberta and migrated to the north and east for over 100 km during the Laramide Orogeny, which was responsible for the uplift of the Rocky Mountains. Biodegradation is the only process that transforms light oil into bitumen in such a dramatic way that overshadowed other alterations with minor contributions. The levels of biodegradation in the basin increasing from west （non-biodegraded） to east （extremely biodegraded） can be attributed to decreasing reservoir temperature, which played the primary role in controlling the biodegradation regime. Once the reservoir was heated to approximately 80℃, it was pasteurized and no biodegradation would further occur. However, reservoir temperature could not alone predict the variations of the oil composition and physical properties. Compositional gradients and a wide range ofbiodegradation degree at single reservoir column indicate that the water-leg size or the volume ratio of oil to water is one of the critical local controls for the vertical variations ofbiodegradation degree and oil physical properties. Late charging and mixing of the fresh and degraded oils ultimately dictate the final distribution of compositions and physical properties found in the heavy oil and oil sand fields. Oil geochemistry can reveal precisely the processes and levels that control these variations in a given field, which opens the possibility of model-d     

两种油砂加工方法的对比研究

分别采用溶剂萃取法和流化热转化法对内蒙古图牧吉油砂的加工方法进行了研究。溶剂萃取法可以得到油砂中几乎所有油品,但其液体产品具有高密度、高黏度及高残炭等特点,后续加工难度大;流化热转化法可以得到油砂中82.3%的油品,与溶剂萃取法相比,其液体产品的性质得到了较大程度的改善。对流化热转化得到的液体产品进行分馏和分析,其中汽油、柴油收率之和达到了37.32%,但是需要进一步精制才能达到国家油品标准的质量要求;重油收率达到了62.68%,可以通过进一步掺炼实现其轻质化。     

COMPARATIVE STUDY OF THE COMPOSITIONAL CHARACTERISTICS OF LIQUIDS DERIVED BY HYDROTREATING OF NIGERIAN TAR SAND BITUMEN. I. SIMULATED DISTILLATION

ABSTRACT

Nigerian tar sand bitumen was hydrotreated at relatively low temperatures and initial hydrogen pressures. The liquid products derived from the hydrotreating process were characterized by the means of instrumental analysis of simulated distillation on gas chromatography. Results show that the liquid products are amenable to the characterization procedure and provided basic data that should be useful in formulating refining processes for Nigerian tar sand bitumen and the liquids derived from its hydrotreating operations. The liquids show differences in products distribution for different temperature but have almost identical structures for same temperatures and different pressures. Generally, increase in temperature caused an increase in conversion of bitumen to distillable products. The characterization data of the derived liquid products will serve as a basis for the identification of processes for upgrading bitumen and such other fossil fuels like coal liquids or heavy vacuum residua.     

FURTHER INVESTIGATIONS ON THE USE OF BITUMEN AND HEAVY OILS TO PROCESS COAL

ABSTRACT

The use of oil sands bitumen, heavy oil and liquids derived therefrom can be successfully used to liquefy an Alberta subbituminous B coal. The data indicate that by co-processing coal with these solvents, coal conversions and yields of liquid products are favorably compared with those obtained using anthracene oil as solvent.     

Tar mats and residual oil distribution in a giant oil field offshore Abu Dhabi

This paper describes how geochemical data (Rock Eval analysis, SARA composition) combined with wireline log interpretation allows for the recognition of the distribution and continuity of bitumens in a main reservoir of an offshore giant field in Abu Dhabi. The integration of new geochemical data with data and field information provided by the oil company ZADCO allows for the recognition of two types of bitumen rich levels in the main reservoir of the field: a) one corresponding to bitumen rich main reservoir intervals associated with high resistivity and high oil saturation, these intervals can be called “tar mats”, b) the other corresponding to low oil saturated intervals, and can be classified as “heavy residual oil”.In terms of lateral and vertical distribution, the tar mats are found at the crestal area of the Present-day structure and are located at the base of the reservoir unit above a tight limestone which plays a role of being a vertical permeability barrier. The tar mats seem to be independent of the Present-day OWC and are not related to biodegradation processes. The heavy residual oil is mainly located in the Northeast and the Southeast parts of the field and close to the OWC but it is also present all around the field except 1) in the west, in the area of the spill point and 2) in the Northwest area where direct contact between mobile oil and water is detected.Study of the structural evolution demonstrates that a tilting of the field began at Dammam age time (Eocene). The tilting of the structure led to a reduction of the structural closure in the West followed by the leakage of part of the originally trapped oil.Numerical modeling of such a geological scenario leads to a distribution of fluids (water, movable oil and residual oil) very close to the one observed at Present-day time in the field. This modeling allows a prediction of the extension and distribution of the residual heavy oil within the studied reservoir and can be used to better define an optimal production scheme. The effects of the residual heavy oils on the fluid circulation are difficult to evaluate, depending on the distribution of the bitumen in the pore network.     

COMPARATIVE STUDY OF THE COMPOSITIONAL CHARACTERISTICS OF LIQUIDS DERIVED BY HYDROTREATING OF NIGERIAN TAR SAND BITUMEN. I. SIMULATED DISTILLATION

Nigerian tar sand bitumen was hydrotreated at relatively low temperatures and initial hydrogen pressures. The liquid products derived from the hydrotreating process were characterized by the means of instrumental analysis of simulated distillation on gas chromatography. Results show that the liquid products are amenable to the characterization procedure and provided basic data that should be useful in formulating refining processes for Nigerian tar sand bitumen and the liquids derived from its hydrotreating operations. The liquids show differences in products distribution for different temperature but have almost identical structures for same temperatures and different pressures. Generally, increase in temperature caused an increase in conversion of bitumen to distillable products. The characterization data of the derived liquid products will serve as a basis for the identification of processes for upgrading bitumen and such other fossil fuels like coal liquids or heavy vacuum residua.     

Road bitumen's based on the vacuum residue of heavy oil and natural asphaltite: Part II – physical and mechanical properties

This work is devoted to studying the possibility of producing bitumen for road construction by using vacuum residue >420°C of heavy oil of the Ashal'chinskoe field in and natural asphaltite Spiridonovskoe field from Permian deposits in Tatarstan. The effect of natural asphaltite as a solid disperse phase element on the structural and group composition of the residual heavy oil product and its malacometrical qualities (penetration, extensibility, softening point, resistance to aging and adhesion) are revealed. Samples, compounded bitumen production, were carried out by introducing the required amount of the shredded asphaltite to deasphaltizat vacuum residue of heavy oil and heating their mixture to 220°С with vigorous stirring. Changes in the composition and physical and chemical properties of deasphalting the residual heavy oil product, associated with the amount of injected asphaltite, showed the possibility of production of modified bitumen with better adhesion properties that correspond to road bitumen.     

内蒙古图牧吉油砂流化热转化反应规律

 在小型流化热转化实验装置上,考察了内蒙古图牧吉油砂的流化热转化反应规律。得到最佳的反应条件为反应温度490℃、反应时间5 min、水/油质量比0.4、热载体/油砂质量比2。在此最优操作条件下,液体产品收率达到79.87%, 轻油收率达到26.59%。随着图牧吉油砂流化热转化反应温度的升高,干气、液化气及汽油产率增加,这主要来自于重油的二次裂化。热转化后的液体产品相对于油砂沥青,残炭、微量金属含量及黏度都有大幅度的降低,同时馏程得到很大改善,有助于后续的加工利用。     

FURTHER INVESTIGATIONS ON THE USE OF BITUMEN AND HEAVY OILS TO PROCESS COAL

The use of oil sands bitumen, heavy oil and liquids derived therefrom can be successfully used to liquefy an Alberta subbituminous B coal. The data indicate that by co-processing coal with these solvents, coal conversions and yields of liquid products are favorably compared with those obtained using anthracene oil as solvent.     

Heavy oil upgrading: Unlocking the future fuel supply

Currently, more than half of the oil reserves (53.3%) in the world are in the form of restorable oils such as heavy oil, extra heavy oil, oil sand, tar sands, oil shale, and bitumen. Heavy oil is one of the petroleum oil varieties that contain long chain hydrocarbons. All types of heavy oils contain asphaltenes and thus are considered very dense substances. The asphaltenes are one of the most complex and heavy organic compounds present in the heavy oil. The heavy oil is defined as one having an American Petroleum Institute scale index equal or smaller than 20°. In conventional refining procedures, heavy oil poses many challenges. Recycling and re-refining are applied techniques for the processing of petroleum based heavy oils into reusable light oils such as gasoline and diesel fuel. In this regard, catalytic pyrolysis and thermal cracking are promising technologies for light oil production. The authors review the heavy oil upgrading processes and their associated challenges with ambition to find cost-effective ways to ensure a constant future fuel supply.     

Road bitumen's based on the vacuum residue of heavy oil and natural asphaltite: Part I – chemical composition

This work is devoted to studying the possibility of producing bitumen for road construction by using vacuum residue >420°C of heavy oil of the Ashal'chinskoe field in and natural asphaltite Spiridonovskoe field from Permian deposits in Tatarstan. The effect of natural asphaltite as a solid disperse phase element on the structural and group composition of the residual heavy oil product and its malacometrical qualities (penetration, extensibility, softening point, resistance to aging and adhesion) is revealed. The production of samples of compounded bitumen production was carried out by introducing the required amount of the shredded asphaltite to deasphaltizat vacuum residue of heavy oil and heating their mixture to 220°С with vigorous stirring. Changes in the composition and physical and chemical properties of deasphalting the residual heavy oil product, associated with the amount of injected asphaltite, showed the possibility of production of modified bitumen with better adhesion properties that correspond to road bitumen.     

CATALYTIC TREATMENT OF HAMMAM AL-ALIL BITUMEN USING NICKEL HEXANOATE

Abstract

Ham mam Al-Alil bitumen (HAB) is found in the Hammam Al-Alil area. The bitumen obtained from this area was found to be mixed with sand, sulfur and sedimentation. Purification of the sample from foreign materials was fulfilled. Asphaltenes were removed by treatment with heptane and the petrolenes obtained were eatalytically cracked using nickel hexanoate and ethanol. The study revealed the heavy nature of such bitumen and supported the idea of the geological and chemical information that deals with Mishraq sulfur deposit and the Qaiyarah crude oil; i.e., Hammam Al-Alil bitumen is Qaiyarah crude oil, which was reduced by Mishraq sulfur. The study of the carbon distributions was carried out using pmr spectroscopy and employing various equations with modification used by previous workers.     

STRUCTURAL FEATURES OF ATHABASCA BITUMEN RELATED TO UPGRADING PERFORMANCE

ABSTRACT

Using a combination of instrumental and chemical methods many new classes of compounds appearing as homologous series have been detected in Athabasca oil sand bitumen and in the chemical and thermal degradative products of asphaltene and the heavy ends of maltene. In general, the volatile portion of the maltene is rich in cyclic terpenoid structures and devoid in aliphatic compounds or normal alkane-derived cyclic molecules while the asphaltene fraction and heavy ends of maltene are abundant in normal alkyl-substituted aromatics, thianes, thiolanes, thiophenes, benzo- and dibenzothiophenes

Ru(VM)-catalyzed oxidation permitted the quantitative estimation of the n-alkyl groups attached to aromatic carbons and of n-alkyl bridges between two aromatic units and their concentration distribution according to chain length. It also showed the presence of a large naphthenic core containing cyclic sulfides, which, during oxidation, were converted to their sulfones.     

CATALYTIC TREATMENT OF HAMMAM AL-ALIL BITUMEN USING NICKEL HEXANOATE

Ham mam Al-Alil bitumen (HAB) is found in the Hammam Al-Alil area. The bitumen obtained from this area was found to be mixed with sand, sulfur and sedimentation. Purification of the sample from foreign materials was fulfilled. Asphaltenes were removed by treatment with heptane and the petrolenes obtained were eatalytically cracked using nickel hexanoate and ethanol. The study revealed the heavy nature of such bitumen and supported the idea of the geological and chemical information that deals with Mishraq sulfur deposit and the Qaiyarah crude oil; i.e., Hammam Al-Alil bitumen is Qaiyarah crude oil, which was reduced by Mishraq sulfur. The study of the carbon distributions was carried out using pmr spectroscopy and employing various equations with modification used by previous workers.     

非生物(无机)成因油气基础科学问题

为了更好地了解原油、沥青的成因,对克拉玛依油田沥青、塔里木盆地干酪根和沥青、辽河油田下第三系干酪根和沥青A以及原油进行了Pb、Sr、N d同位素研究,结果表明:准噶尔、塔里木和辽河3个盆地的沥青及原油的Pb同位素均显示出了壳-幔相互作用的特征,也均表现出不同于干酪根Pb同位素组成的特征(干酪根的Pb同位素组成明显表现出壳源的特征);克拉玛依沥青的Rb-Sr等时线年龄及初始Sr比值(87Sr/86Sr)I(即IO)与达尔布特断裂带附近金矿的成矿年龄和IO相一致,表明沥青与金矿的金均来自相同的深部源区。指出在准噶尔盆地通过深部地震测深所获得的中地壳低速层存在的信息支持了这样一个假说,油气可能为非生物(无机)成因。     

A PHYSICAL CHEMICAL EXPLANATION FOR DETERIORATION IN THE HOT WATER PROCESSABILITY OF ATHABASCA OIL SAND DUE TO AGING

ABSTRACT

The oxidation of sulphide minerals during storage of Athabasca oil sands causes solubilization of inorganic salts which affect recovery of bitumen during hot water extraction. DLVO and Ionizable Surface Group Model theories accurately predict that the level of soluble salts produced is sufficient to cause coagulation of the fine particles during the process which leads to a deterioration in froth quality and loss of bitumen recovery. The rate of aging is specific to each oil sand but storage of oil sands under an inert atmosphere in air-tight container at sub-zero temperatures will minimize oxidation.     

The steric hardening and structuring of paraffinic hydrocarbons in bitumen

The formation of ordered structures of macro- and microcrystalline waxes during cooling from the melt of bitumen was observed using temperature-modulated differential scanning calorimetry. This process develops in time. It is found that steric hardening of bitumen (gradual hardening at room temperature) is related to the processes of formation of ordered structures of bitumen waxes.