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.     

加拿大Athabasca油砂中部分沥青质油不易分离的原因

1. Introduction Commercial recovery of bitumen from oil sands iscurrently achieved by means of water based separationprocesses. While most of these separation methods arebased on the Hot Water Extraction Process, the need toconserve energy has resulted …     

油砂沥青油的加工利用

利用溶剂抽提分离油砂沥青,比较了油砂沥青油的沸腾床加氢实验和焦化实验,以及油砂的干馏实验。结果表明,以甲苯为溶剂抽提分离油砂沥青,可使沥青油回收超过90%。油砂沥青油具有密度大、灰分高、盐含量高的特点,胶质沥青质质量分数超过90%。采用沸腾床加氢处理脱盐沥青油,可使其硫、残炭、镍、钒的脱除率分别达到7283%、6685%、9616%和9824%,胶质和沥青质的转化率分别为7353%和9863%,加氢产物是优质的深加工原料。采用焦化处理非脱盐沥青油,总液收6164%,焦炭产率2895%,资源相对有效利用率低。油砂直接干馏,沥青油总回收率只有7856%。从油砂沥青油的有效回收和利用上看,沸腾床加氢是最有效的手段。     

油砂中沥青的热碱水萃取分离及其影响因素

油砂作为非常规石油资源,在能源需求不断增加和石油价格持续走高的情形下将成为重要的接替能源之一.研制了一套热碱水萃取分离装置,对中国2个地区的油砂开展了沥青的热碱水分离实验,探讨了分离过程中温度和碱的加入量、通气条件及加工助剂等因素对沥青有效分离的影响.内蒙古扎赉特旗油砂的分离实验结果表明,随着萃取热碱水温度的升高,浮选...     

13NMR CHARACTERIZATION OF HUMIC MATTER PRESENT IN DIFFERENT OIL SANDS

Insoluble organic matter (humic matter) present in oil sands can alter the wettability of the inorganic matrix and thereby cause serious problems during bitumen recovery.

Using a cold water agitation test, solids rich in organic matter were isolated from various oil sands which were chosen to reflect different behavior in the hot water extraction process.¹³C NMR examination of these separated solids showed significant structural variations between samples isolated from different oil sands. Humic matter from Utah oil sand appeared to be more aliphatic than that derived from Athabasca oil sand.

Humic acids extracted from organic rich solids as a result of prolonged treatment with 2% NaOH show remarkable similarity in their ¹³C NMR spectra. Humins differ substantially in the relative contribution of the terrestrial and marine source material. There was apparent correspondence between poor bitumen separation and the presence of humin with highly paraffinic structures.     

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.     

13NMR CHARACTERIZATION OF HUMIC MATTER PRESENT IN DIFFERENT OIL SANDS

ABSTRACT

Insoluble organic matter (humic matter) present in oil sands can alter the wettability of the inorganic matrix and thereby cause serious problems during bitumen recovery.

Using a cold water agitation test, solids rich in organic matter were isolated from various oil sands which were chosen to reflect different behavior in the hot water extraction process.¹³C NMR examination of these separated solids showed significant structural variations between samples isolated from different oil sands. Humic matter from Utah oil sand appeared to be more aliphatic than that derived from Athabasca oil sand.

Humic acids extracted from organic rich solids as a result of prolonged treatment with 2% NaOH show remarkable similarity in their ¹³C NMR spectra. Humins differ substantially in the relative contribution of the terrestrial and marine source material. There was apparent correspondence between poor bitumen separation and the presence of humin with highly paraffinic structures.     

The Comparison of Bitumens from Oil Sands with Different Recovery Profiles

Abstract

It has been proposed that, regardless of origin, the recovery of bitumen from oil sands is related to its viscosity. Asphaltene and resin contents are known to affect the viscosity of bitumen. In this article we compare the composition of solvent-extracted bitumens from several Athabasca oil sands with very different recovery profiles. After careful removal of any associated mineral matter by ultra-centrifugation, each bitumen sample was separated into saturate, aromatic, resin, and asphaltene (SARA) fractions by an enhanced SARA technique. The individual components were then characterized by several complementary analytical techniques, including carbon, nitrogen, nitrogen, sulfur, size exclusion chromatography molecular weight (MW_n) plus proton and ¹³C nuclear magnetic resonance spectroscopy. Based on this comparison, we see no correlation between the recovery of bitumen and its composition.     

使用ASP试剂从印尼油砂中回收沥青

通过使用自制的ASP试剂从印尼油砂中回收沥青,研究了油砂沥青的分离条件。结果表明适宜的分离条件如下：混合温度80℃、混合时间40min、ASP试剂与油砂的质量比为4:10、浮选时间10min,在上述条件下,沥青回收率可达86%,尾砂中沥青残余率为6%。为了进一步降低尾砂的含油量,研究了尾砂中沥青含量与尾砂粒径的关系,结果表明：随着尾砂粒径的减小,尾砂的含油量降低。对尾砂研磨30min后,采用ASP试剂抽提法进一步处理,尾砂的含油量由5.47% 降到1.25%,符合排放要求。     

MINERAL MATTER AND CLAY-ORGANIC COMPLEXES IN OIL SANDS EXTRACTION PROCESSES

ABSTRACT

Differences in oil sands processability and extraction yields can be dependent upon many factors including the composition of the mineral components and the organic complexes that are associated with certain minerals. These mineral-organic associations help provide the bridge which leads to carry over of bitumen with the tailings as well as carry over of water and mineral matter with the bitumen product. The nature of the organic component of clay-organic complexes extracted from various streams in an oil sands recovery process is discussed in relation to the stability of both water-in-oil and oil-in-water emulsions formed.

The samples were obtained from Suncor's oil sands extraction plant located in Fort McMurray, Alberta. Samples were obtained from throughout the extraction process from the primary froth through to the final diluted bitumen product. These samples have been studied with nuclear magnetic resonance (NMR), scanning electron microscopy (SEM) as well as with other techniques such as interfacial tension measurements. The data indicates that high water content products originate, to a great extent, from the presence of a very hydrophilic organic matrix attached to the surface of the clay and heavy metal minerals.     

High-efficiency Extraction of Bitumen from Oil Sands Using Mixture of Ionic Liquid [Emim][BF4] and Dichloromethane

An ionic liquid (IL), 1-ethyl-3-methyl imidazolium tetrafluoroborate ([Emim][BF4]), was used to enhance bitumen recovery from oil sands by dichloromethane solve...     

MINERAL MATTER AND CLAY-ORGANIC COMPLEXES IN OIL SANDS EXTRACTION PROCESSES

Differences in oil sands processability and extraction yields can be dependent upon many factors including the composition of the mineral components and the organic complexes that are associated with certain minerals. These mineral-organic associations help provide the bridge which leads to carry over of bitumen with the tailings as well as carry over of water and mineral matter with the bitumen product. The nature of the organic component of clay-organic complexes extracted from various streams in an oil sands recovery process is discussed in relation to the stability of both water-in-oil and oil-in-water emulsions formed.

The samples were obtained from Suncor's oil sands extraction plant located in Fort McMurray, Alberta. Samples were obtained from throughout the extraction process from the primary froth through to the final diluted bitumen product. These samples have been studied with nuclear magnetic resonance (NMR), scanning electron microscopy (SEM) as well as with other techniques such as interfacial tension measurements. The data indicates that high water content products originate, to a great extent, from the presence of a very hydrophilic organic matrix attached to the surface of the clay and heavy metal minerals.     

柴达木盆地西部侏罗系油砂的发现及其意义

最近在柴达木盆地西部阿尔金断裂南侧地面剖面上侏罗统地层中首次发现了厚约90m的油砂及大量裂缝沥青脉。通过对这些油砂和沥青的分析研究发现,它们与柴达木盆地西部第三系原油差别较大,与柴达木盆地东部侏罗系原油较相似但也有一定差异。野外地质调查发现柴达木盆地西北部发育大量侏罗系烃源岩,其生物标志物等特征与这些油砂和沥青相似,综合分析认为这些油砂和沥青脉可能来源于成熟的侏罗系源岩。这些油砂的发现对柴达木盆地西北部及阿尔金断裂沿线盆地的油气勘探具有重要意义。     

MANAGEMENT OF OIL SANDS TAILINGS

In Alberta, oil sands bitumen is utilized for synthetic crude oil (SCO) production by surface mining, bitumen extraction followed by primary (coking) and secondary (catalytic hydrotreating) upgrading processes. SCO is further refined in specially designed or slightly modified conventional refineries into transportation fuels. Oil sands tailings, composed of water, sands, silt, clay and residual bitumen, is produced as a byproduct of the bitumen extraction process. The tailings have poor consolidation and water release characteristics. For twenty years, significant research has been performed to improve the consolidation and water release characteristics of the tailings. Several processes were developed for the management of oil sands tailings, resulting in different recovered water characteristics, consolidation rates and consolidated solid characteristics. These processes may affect the performance of the overall plant operations. Apex Engineering Inc. (AEI) has been developing a process for the same purpose. In this process oil sands tailings are treated with Ca(OH)₂ lime and CO₂ and thickened using a suitable thickener. The combination of chemical treatment and the use of a thickener results in the release of process water in short retention times without accumulation of any ions in the recovered water. This makes it possible to recycle the recovered water, probably after a chemical treatment, as warm as possible, which improves the thermal efficiency of the extraction process. The AEI Process can be applied in many different fashions for the management of different fractions of the tailings effluent, depending on the overall plant operating priorities.     

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

Abstract

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.     

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.     

Oil sand processing by ultrasonic technique

The kinetics of bitumen (asphalt), oil, and residual fuel oil extraction from oil sands by ultrasonic treatment has been studied. The influence of the working temperature of the process, characteristics of the separated components, fineness of the solid phase, and additive concentration on the extraction rate has been investigated. A schematic diagram of the installation for oil sands processing using an ultrasonic reactor is given. It is shown that ultrasonic devices could be an alternative to the presently used industrial equipment for bitumen and oil products extraction from oil-bearing rocks and oil sludge.     

MANAGEMENT OF OIL SANDS TAILINGS

ABSTRACT

In Alberta, oil sands bitumen is utilized for synthetic crude oil (SCO) production by surface mining, bitumen extraction followed by primary (coking) and secondary (catalytic hydrotreating) upgrading processes. SCO is further refined in specially designed or slightly modified conventional refineries into transportation fuels. Oil sands tailings, composed of water, sands, silt, clay and residual bitumen, is produced as a byproduct of the bitumen extraction process. The tailings have poor consolidation and water release characteristics. For twenty years, significant research has been performed to improve the consolidation and water release characteristics of the tailings. Several processes were developed for the management of oil sands tailings, resulting in different recovered water characteristics, consolidation rates and consolidated solid characteristics. These processes may affect the performance of the overall plant operations. Apex Engineering Inc. (AEI) has been developing a process for the same purpose. In this process oil sands tailings are treated with Ca(OH)₂ lime and CO₂ and thickened using a suitable thickener. The combination of chemical treatment and the use of a thickener results in the release of process water in short retention times without accumulation of any ions in the recovered water. This makes it possible to recycle the recovered water, probably after a chemical treatment, as warm as possible, which improves the thermal efficiency of the extraction process. The AEI Process can be applied in many different fashions for the management of different fractions of the tailings effluent, depending on the overall plant operating priorities.     

加拿大油砂溶剂提取分离的实验研究

采用半连续溶剂抽提法对加拿大油砂进行了提取分离试验,应用溶解度参数理论以及实验筛选出最佳抽提溶剂为重整汽油。综合考察了提取温度、溶剂流量、提取时间以及提取压力等工艺操作条件对油砂沥青提取的影响。结果表明,在提取温度80 ℃、溶剂流量60 mL/min、提取时间60 min、提取压力1.0 MPa的条件下,油砂沥青提取率达到92.74%。     

油砂沥青油的加氢处理研究

油砂沥青油为高密度、高黏度、高金属含量、高残炭的劣质原料,采用沸腾床加氢催化剂,利用反应釜进行加氢处理,考察了反应温度和反应时间对其反应性能的影响,以寻求最佳的沸腾床加氢处理反应条件。实验结果表明,随着反应温度升高、反应时间增加,油砂沥青油的加氢生成油中Fe,Na,Ni,V含量和残炭逐渐降低,最佳反应条件为反应温度430 ℃、反应时间80min,在该条件下,Fe,Na,Ni,V的脱除率分别为99.97%,99.99%,98.11%,99.61%,残炭降低率为72.61%。利用沸腾床进行油砂沥青油的加氢处理,可以有效改善油品性质,满足深加工要求。