Distribution of clay minerals in the process streams produced by the extraction of bitumen from Athabasca oil sands

This study investigates the affinity of clay minerals in oil sands for the water‐continuous tailings and hydrocarbon‐continuous froth streams produced from the extraction of bitumen from oil sands. Clay minerals in oil sands processing impact bitumen flotation in separation vessels, emulsion formation during froth treatment, and fine tailings behaviour. X‐ray diffraction of oriented clay slides and random powder samples were used to quantify the clay minerals in the oil sands ore and process streams. Particle size distribution and clay activity balances were also conducted around the extraction process. The degree of partitioning during the conditioning and flotation stages in a batch extractor was determined by the surface properties of the clay minerals present. The water‐continuous tailings stream was further separated into fine and coarse tailings fractions through sedimentation. The bulk of the clay minerals reported to the fine tailings stream. Illite and mixed layered illite‐smectite partitioned less to the hydrocarbon‐continuous froth than kaolinite. Also, the illite‐smectite in the froth stream appeared to be different from the illite‐smectite in the water continuous streams.     

Wettability of fine solids extracted from bitumen froth

Production of synthetic crude oil from oil sands deposits in northern Alberta involves open pit mining, mixing the mined ore with water, extraction of aerated bitumen from the slurry, removal of water and solids from the froth formed, and upgrading heavy bitumen to liquid hydrocarbons. The success of the froth treatment operation, aimed at removal of fine solids and water from the bituminous froth, depends on the control of wettability of fine solids by the aqueous phase. Fine solids were extracted from bitumen froth by heptane. The partition of the extracted solids in aqueous, organic, and interphases was measured, and the wettability of the solids by water in various diluents was evaluated from contact angle measurements. The effect of diluent composition, sample drying, and surface washing on the wettability and fine particle partition was examined. The partition of fine particles correlated well with their wettabilities, and the results were found to be useful for interpreting the observations from froth treatment practice.     

Determination of clay content in Canadian oil sands using x-ray florescence spectroscopy for diagnosis of ore processability

In this study, a simple and robust method based on the use of x-ray fluorescence (XRF) spectroscopy to measure potassium content as an indicator of illite in oil sands was proposed and tested. The XRF results of illite determination were compared with those determined using the conventional methylene blue titration (MBT) method. To test the suitability of the XRF method for determining illite content in various streams of oil sands processing as a diagnosis tool, a toluene-diluted-bitumen solution was used to contaminate solid surfaces prior to their analysis by the XRF and MBT methods. In order to remove the organic matter from the bitumen-contaminated solids for evaluating the XRF and MBT method, toluene washing and low temperature ashing were applied to the bitumen-contaminated solids prior to their analysis. The robustness of the XRF analysis in comparison with the MBT method was further confirmed by analyzing the solids extracted from bitumen froth and tailings stream. The results show that the XRF method was more tolerant to surface contamination and therefore more reliable in determining illite content in oil sands and relevant processing streams. It was also found that the potassium contents measured by the XRF method on solids from 10 ores show a strong correlation with the corresponding fines contents of these ores, indicating that the XRF method can potentially be used to determine the fines content of oil sands and related processing streams.     

Solvent screening for non‐aqueous extraction of Alberta oil sands

Non‐aqueous extraction of bitumen from oil sands has the potential to reduce fresh water demand of the extraction process and eliminate tailings ponds. In this study, different light hydrocarbon solvents, including aromatics, cycloalkanes, biologically derived solvents and mixtures of solvents were compared for extraction of bitumen from Alberta oil sands at room temperature and ambient pressure. The solvents are compared based on bitumen recovery, the amount of residual solvent in the extracted oil sands tailings and the content of fine solids in the extracted bitumen. The extraction experiments were carried out in a multistage process with agitation in rotary mixers and vibration sieving. The oil sands tailings were dried under ambient conditions, and their residual solvent contents were measured by a purge and trap system followed by gas chromatography. The elemental compositions of the extraction tailings were measured to calculate bitumen recovery. Supernatants from the extraction tests were centrifuged to separate and measure the contents of fine solid particles. Except for limonene and isoprene, the tested solvents showed good bitumen recoveries of around 95%. The solvent drying rates and residual solvent contents in the extracted oil sands tailings correlated to solvent vapour pressure. The contents of fine solids in the extracted bitumen (supernatant) were below 2.9% for all solvents except n‐heptane‐rich ones. Based on these findings, cyclohexane is the best candidate solvent for bitumen extraction, with 94.4% bitumen recovery, 5 mg of residual solvent per kilogram of extraction tailings and 1.4 wt% fine solids in the recovered bitumen. © 2012 Canadian Society for Chemical Engineering     

Understanding weathering of oil sands ores by atomic force microscopy

Effect of weathering on colloidal interactions between bitumen and oil sands solids was studied by atomic force microscopy (AFM). The change in bitumen chemistry due to weathering was found to have a negligible effect on the interactions of bitumen with solid particles. However, the increase in solid surface hydrophobicity due to ore weathering reversed the long‐range interaction forces between bitumen and solids from repulsive to attractive with a corresponding increase in adhesion force. The measured force profiles between bitumen and various solids can be well fitted with the extended DLVO theory by considering an additional attractive force. The attractive long‐range force and increased adhesion force make the separation of bitumen from solids more difficult and the attachment of fine solids on liberated bitumen easier, thereby leading to poor bitumen liberation and lower aeration efficiency. Such changes account for the observed poor processability of the weathered ores. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Role of mineral flotation technology in improving bitumen extraction from mined Athabasca oil sands: I. Flotation chemistry of water‐based oil sand extraction

The role of surface hydrophobicity in water‐based oil sand extraction is examined from the perspective of mineral flotation separation. Although anionic carboxylates (sulphonates) released from bitumen are helpful for charging bitumen and liberating bitumen from sand grains, their presence in oil sand slurries tends to make bitumen and bubbles less hydrophobic. In addition, solid hydrophobization under oil sand extraction conditions can occur through different mechanisms of carboxylate adsorption. It is the hydrophobized fine solids that present challenges for achieving a high bitumen recovery with a good froth quality, due to their competition with bitumen for attachment to bubbles. While chemisorption of carboxylates contributes to hydrophobization of heavy minerals present in oil sands, carboxylate adsorption activated by hydrolyzed metal cations alters silica and clays from hydrophilic to hydrophobic. Different adsorption mechanisms of calcium on silica, clays, and other minerals are analyzed to explain why fine solids of varying mineralogy in combination with calcium affect bitumen extraction differently. Metal ions that activate solid hydrophobization under oil sand extraction conditions are identified from dynamic attachment of solids from mature fine tailings (MFT) to bitumen. To mitigate the effect of fines on oil sand extraction, selective flocculation of fine solids is recognized as especially feasible for bitumen flotation recovery from oil sand middling streams. Future research in reducing or eliminating caustic addition, understanding the role of inorganic anions, and searching for feasible techniques for treating MFT based on different mineralogy and surface properties, are briefly discussed.

     

Effect of natural surfactants released from athabasca oil sands on air holdup in a water column

Natural surfactants released from Athabasca oil sands are a crucial component in water‐based bitumen extraction processes. The effect of natural surfactant released from estuarine and marine oil sands on air holdup was investigated using a water column. The air holdup in the resultant supernatant of the conditioned oil sands slurry was found to be much higher than that in de‐ionized water. A further increase in air holdup was observed with the supernatant obtained from the oil sands slurry conditioned with caustic. Aging of the ore prior to bitumen extraction caused an increase in air holdup. The presence of small amount of fine solids in the supernatant resulted in a higher air holdup for all the cases studied. The present study shows that the higher air holdup and poorer processibility of marine ores, compared with estuarine ores, could be accounted for by the release of larger amount of surface active species and the presence of more fine clays in the ores.     

Effect of weathering on oil sands processability

Effect of weathering on oil sand processability was studied using a good processing ore, a laboratory weathered ore and a naturally weathered ore. The laboratory weathered ore was prepared by weathering the good processing ore in an oven under controlled conditions to study the nature of ore weathering. It was found that the bitumen recovery, bitumen flotation rate, and bitumen froth quality were greatly reduced due to ore weathering. It was also observed that the fresh bitumen coating on a silicon surface could recede and liberate from the silicon surface easily even in a warm water of 35°C. However, after weathering of the bitumen coating, its liberation became more difficult and effective liberation of bitumen from the silicon surface could only occur at higher temperature of 65°C. The current study further confirms that weathering enhanced adhesion of bitumen with solids, causing difficulties for bitumen liberation from sand grains and hence poor processability of weathered ores.     

Effect of molecular weight and charge density on the performance of polyacrylamide in low‐grade oil sand ore processing

The effect of charge density and molecular weight (MW) of partially hydrolyzed polyacrylamide (HPAM) polymers on their performance in processing low‐grade oil sand ores was investigated. Bitumen extraction and tailings settling tests were carried out and an atomic force microscope (AFM) was used to directly measure the bitumen‐solid and solid‐solid interaction forces. It was found that HPAM polymers with a low MW acted as dispersants in the bitumen extraction process, resulting in low bitumen recovery and slow tailings settling but improved froth quality. In contrast, the use of HPAM polymers with a high MW improved both bitumen recovery and tailings settling but deteriorated froth quality. To achieve high bitumen recovery and fast tailings settling, a HPAM polymer must have a low to medium charge density (～30%) and a high MW (17.5 million Daltons). A stronger clay‐bitumen adhesion force normally resulted in a lower bitumen recovery. Fast tailings settling was achieved in the presence of a strong solid‐solid adhesion force.     

Organic coated solids in athabasca bitumen: Characterization and process implications

Bitumen, separated from oil sands by the hot water extraction process, contains ultra‐fine (< 200 nm), inorganic solids (BS). Surfaces of BS particles are coated with toluene insoluble organic matter (TIOM). This organic material is polar and aromatic with contributions from both humic and asphaltene‐like components. Although the surfaces of BS particles are dominated by TIOM, the coverage is patchy rather than continuous. As a result, these solids are capable of stabilizing fine water emulsions in the bitumen phase. The nature of the organic matter on the surfaces of the particles is such that it has a high propensity to form coke. Therefore, these particles can also play a role in fouling on equipment and catalysts.     

Separation and Characterisation of Problematic Solids from Athabasca Oil Sands and Waste Unit Samples

Traditionally, Athabasca oil sands have been classified by bitumen and fines (<44 µm) contents. However, these markers do not always identify ores with poor processing characteristics. Consequently, there is a need to discover other characteristics to define problem ores. Here we describe a separation scheme for oil sands solids fractions based on their physical and surface properties. Clay material (<3 µm) and its ultra‐fine (<0.3 µm) component are of particular interest. Settling tests on ultra‐fine clay suspensions confirm that this fraction is the major cause of sludging during primary bitumen separation. Waste units, or barren oil sands, are shown to be a major source of this component.     

Application of microbial enhanced oil recovery technology in water‐based bitumen extraction from weathered oil sands

When using the water‐based extraction processes (WBEPs) to recover bitumen from the weathered oil sands, very low bitumen recovery arisen from the poor liberation of bitumen from sand grains is always obtained. Application of microbial enhanced oil recovery (MEOR) technology in WBEPs to solve the poor processability of the weathered ore was proposed. It was found that processability of the microbial‐treated weathered ore was greatly improved. The improved processability was attributed to the biosurfactants production in the culture solution, alteration of the solids wettability, degradation of the asphaltene component, and the decrease of the bitumen viscosity, which collectively contributed to the bitumen liberation from the surface of sand grains. Although it still has many issues to be solved for an industrial application of the MEOR technology in oil sands separation, it is believed that the findings in this work promote the solution to the poor processability of the weathered ore. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2985–2993, 2014     

Effect of particle size on the rheology of Athabasca clay suspensions

The success of the separation process conventionally used in Alberta for oil sands extraction is highly influenced by the rheology of the oil sands slurry. In the gravity separation vessel, high slurry viscosities can hinder the rise of aerated bitumen and reduce the efficiency of the recovery process. In this study, the effect of particle size on the viscosity of oil sands slurries is investigated. Solids from mature fine tails (MFT) obtained from tailings pond were fractionated into three fractions of different particle size distributions and their rheological properties were studied. The solids in each fraction were characterized by XRD analysis which showed the presence of different types of clays in each fraction. For the rheological measurements, dispersions of the three fractions were prepared in the supernatant water decanted from centrifuged MFT to maintain the solution chemistry of the solids. Suspensions of each fraction showed a non‐Newtonian shear thinning behaviour as well as yield stress that is characteristic of structure formation within the suspensions. For all solids fractions, increasing solids concentration led to higher viscosities and higher yield stress values. Viscoelastic properties of the suspensions showed stronger solid‐like behaviour at higher particle concentrations. Among the three fractions numbered from 1 to 3, solids in fraction 3 were coated with organic matters, exhibiting the highest suspension viscosities. Also for fraction 3, higher gelling potency was observed at much lower weight fractions of solids as compared to the other fractions.     

Understanding Water‐Based Bitumen Extraction from Athabasca Oil Sands

The current state of knowledge on the fundamentals of bitumen recovery from Athabasca oil sands using water‐based extraction methods is reviewed. Instead of investigating bitumen extraction as a black box, the bitumen extraction process has been discussed and analyzed as individual steps: Oil sand lump size reduction, bitumen liberation, aeration, flotation and interactions among the different components that make up an oil sand slurry. With the development and adoption of advanced analytical instrumentations, our understanding of bitumen extraction at each individual step has been extended from the macroscopic scale down to the molecular level. How to improve bitumen recovery and bitumen froth quality from poor processing ores is still a future challenge in oil sands processing.     

Polymer aids for settling and filtration of oil sands tailings

Commercial Magnafloc 1011 (Percol 727) polymer and in‐house synthesised Al‐PAM polymer were used to flocculate oil sands tailings that were derived from low and high fines oil sands ores. Fines are defined as mineral solids less than 44 µm. The performance of polymers was evaluated in terms of tailings settling, filtration rate, and final moisture content of tilter cakes. Both polymers were shown to effectively flocculate the derived oil sands tailings and hence to enhance tailings settling. Al‐PAM performed very well as a filtration aid. The final moisture content of the filter cake obtained from tailings derived from the low fines ore was 6.6 ± 1.2 wt.% and that from the high fines ore was 16.9 ± 0.8 wt.%. This class of polymer can provide an alternative approach for oil sands tailings disposal that has the potential to eliminate tailings ponds. However, the commercial Magnafloc 1011 polymer was found ineffective as a filtration aid for the two tailings tested in this study.     

Effect of ore quality on non-aqueous oil sand extraction performance

Current commercial aqueous based extraction processes are energy and greenhouse gas (GHG) intensive and require large tailings ponds. Non-aqueous extraction (NAE) of bitumen from mineable oil sands is an alternative that eliminates tailings ponds with potentially lower energy requirements and GHG emissions. The economics of the NAE process depend partly on the impact of ore quality on bitumen recovery and product quality (low water and solids content). It has been claimed that NAE performance is insensitive to the quality (bitumen content) of the oil sand ores. However, the available data are ambiguous because different extraction methods and solvents were used in different studies and, in many cases, a limited range of ore qualities was examined. In this study, bitumen was extracted from eight ores of different quality with cyclohexane using a multistage method equivalent to a countercurrent process with a solvent/ore ratio of 0.67 w/w. The bitumen recovery and the water and solids content of the product bitumen were determined for each ore. It was found that bitumen recovery correlated negatively to clay content of the ore. The loss of recovery was attributed to bitumen adsorption on clays. The product quality was insensitive to the ore quality and instead depended on the density of the fluid medium, as expected with a centrifuge-based separation method. The recovery and product quality from the NAE method were similar to those from aqueous extractions.     

Wettability alteration of solid surface to enhance the bitumen liberation and the water-based processability of weathered oil sands

Weathering often induces bituminous materials adsorbing on the sand grains and leads to poor processability of the oil sands. Chemical and microbial pre-treatment of the prepared weathered ore model and a weathered oil sand ore were carried out to improve the solids surface wettability so as to facilitate the bitumen liberation and recovery. It was found that although all the cetyl trimethylammonium bromide (CTAB), sodium dodecylbenzene sulphonate (SDBS), and microbial culture medium could greatly decrease the surface tension of the solution, the CTAB treatment failed to improve the bitumen liberation, while the SDBS and microbial treatment significantly accelerated the bitumen liberation from the silicon substrates. The wettability analysis showed that the improved bitumen liberation could be attributed to the alteration of the solids surface wettability from hydrophobic to hydrophilic by the SDBS and microbial treatment. Inconsistent with the findings of the bitumen liberation, floatation tests of a weathered ore showed that the CTAB pre-treatment only gave a low bitumen recovery of 33%, while the SDBS and microbial pre-treatment improved the processability of the ore. In particular, the microbial treatment was more effective at removing the adsorbed organics from the solids and improved the surface hydrophilicity, resulting in a much better bitumen recovery of 95%. This work provides a way to improve the processability of the weathered ore by altering the solids surface wettability.     

Effect of Operating Temperature on Water‐Based Oil Sands Processing

Operating temperature is one of the most important controlling parameters in oil sands processing. Considering the massive energy consumption and green house gas emission, lowering the processing temperature is highly desirable. To achieve such an ambitious goal requires a comprehensive understanding on the role of temperature in oil sands processing. This paper provides an overview of major findings from existing studies related to oil sands processing temperature. The relation between temperature and bitumen recovery is discussed. The effect of temperature on the physiochemical properties of oil sand components, such as bitumen viscosity, bitumen surface tension and surface potentials of bitumen and solids, is analyzed. The interactions between bitumen and solids and between bitumen and gas bubbles as a function of temperature are recounted. Also discussed is the role of chemical additives in oil sand processing. It has been found that temperature affects nearly all properties of oil sands among which bitumen viscosity and bitumen‐solids adhesion impose a prominent impact on bitumen recovery. The use of selected chemical additives can reduce bitumen viscosity and/or the bitumen‐solids adhesion, and thus provide a possible way to process oil sands at a low temperature while maintaining a high bitumen recovery.     

Characterization of Athabasca oil sands froth treatment tailings for heavy mineral recovery

Titanium (Ti) and zirconium (Zr) minerals (heavy minerals) in the Athabasca oil sands are concentrated in the bitumen froth treatment tailings during the hot water bitumen extraction operations. Recovery processes for these minerals have been explored since the 1970s, yet there is still no established process flowsheet to economically recover these minerals. We recently carried out a research project based on the knowledge of these previous studies. The objective of the project was to study the effect of residual bitumen removal methods from the froth treatment tailings on the separation characteristics of the heavy minerals contained in the tailings. The work reported in this paper is part of the project and it concerns the characterization of the froth treatment tailings. It was found that, rather than burning it off, the residual bitumen in the froth treatment tailings is worth recovering. Separation properties of the heavy minerals contained in the froth treatment tailings were studied by chemical assays, particle size-assay analysis, magnetic susceptibility measurements, gravity and magnetic separation, mineralogical analysis and scanning electron microscope (SEM) analysis coupled with energy dispersive x-ray (EDX) analysis.     

Novel polymer aids for low‐grade oil sand ore processing

In the present study, a hybrid Al(OH)₃‐polyacrylamide (Al‐PAM) was synthesized and used in combination with a partially hydrolyzed polyacrylamide (HPAM) to process a low‐grade oil sand ore. It was found that Al‐PAM was capable to improve bitumen froth quality and tailings settling. But it led to deterioration in bitumen recovery due to the formation of large bitumen lumps during the bitumen extraction process. To resolve this problem, HPAM was added in combination with Al‐PAM as a dual system. The use of the dual system at a low dosage achieved a holistic improvement in bitumen recovery, froth quality, and tailings settling. To understand the role of Al‐PAM and the dual system in the bitumen extraction process, bitumen‐clay, bitumen‐bitumen, and clay‐sand interaction and adhesion forces were directly measured using an atomic force microscope (AFM). The measured forces indicate that bitumen recovery and tailings settling are controlled by the colloidal interaction and adhesion forces between the oil sand components.