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.     

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.     

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.     

Characterization of organic‐coated solids isolated from different oil sands

Solids isolated from weathered oil sands ores and those having low‐ and high‐fine solids content were studied. The organic matter (OM) adsorbed on the solids was found insoluble in most common solvents, contributing significantly to the change of solid surface properties. The surface properties of these solids were found to affect the entire process cycle of obtaining synthetic crude oil from surface‐mined oil sands using a water‐based extraction process, and managing the existing tailings ponds. In this study, the low‐fine solids ore possessed the lowest amount of organic‐coated solids and highest bitumen recovery. Siderite and pyrite, which tend to concentrate in the hydrocarbon phase were observed in the isolated solids from the weathered and high‐fine ores but were absent in the low‐fine ores. In all the ores studied, the solids from the bitumen froth possess less quartz, and more carbonates compared with solids from the tailings. Elemental analysis by energy dispersive X‐ray spectroscopy (EDX) and elemental analyser revealed the presence of more transition metals (iron and titanium), and carbon in the solids obtained from the bitumen froth when compared with those from the tailings. Infrared (IR) spectroscopy study substantiated the results obtained by X‐ray diffraction and elemental analysis. IR spectra showed a likely association between OM and carbonates in the organic‐coated solids isolated from bitumen froth. More organic‐coated solids were found in weathered oil sands than in other types of ores and observed to reduce bitumen recovery from oil sands.     

Polyacrylamides revisited: flocculation of kaolin suspensions and mature fine tailings

A series of acrylamide‐based water‐soluble (co)polymers was synthesized and they were investigated as flocculants of model kaolin suspensions and mature fine tailings of oil sands. The effects of molar mass, charge density, and polymer concentration on flocculation efficiency were studied by monitoring the initial settling rate during sedimentation. Hydrolyzed polyacrylamide (HPAM) with high molar mass and intermediate acrylic acid contents (0.14–0.41 mol/mol (14–41 mol%)) performed better in flocculation tests on kaolin suspensions requiring lower dose for maximum initial settling rate than native polyacrylamide (PAM). Surface force measurements showed that at low polymer concentrations (1 ppm), the partially‐adsorbed polymer induced a bridging attraction between the mica surfaces. Increasing the polymer concentration to 10 and 50 ppm caused purely repulsive forces. The presence of anionic groups in HPAM led to stronger repulsion, which was also demonstrated by the higher viscosity and larger hydrodynamic radius of the charged polymer. The charge‐induced increase in the viscosity of polymer solutions was suppressed by the screening effect of salts in a buffer solution and reducing the viscosity is desirable in the injection of flocculants in the industrial process.     

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.

     

Investigation of Oil Sands Froth Treatment

Two oil sand froth treatment methods are investigated: 1) dilution with an aromatic solvent followed by centrifugation (AS Method); 2) dilution with a paraffinic solvent followed by gravity settling (PS Method). The effectiveness of the methods is assessed in terms of bitumen recovery and the water content in the recovered diluted bitumen. The optimum solventto‐bitumen ratios are identified considering process type, ore quality, temperature, and residence time.     

Development of a vision‐based online soft sensor for oil sands flotation using support vector regression and its application in the dynamic monitoring of bitumen extraction

Extraction from oil sands is a crucial step in the industrial recovery of bitumen. It is challenging to obtain online measurements of process outputs such as bitumen grade and recovery. Online measurements are a prerequisite for innovating better process control solutions for process efficiency and cost reduction. We have developed a soft sensor to provide online measurements of bitumen grade and recovery in a flotation‐based oil sand extraction process. Continuous froth images were captured using a VisioFroth camera system on a batch flotation unit. A support vector regression (SVR) model with a Gaussian kernel was constructed to develop a soft sensor for bitumen grade and recovery using froth image features as the inputs. The model was trained and validated for batch flotation of different grades of oil sands ore at industry‐relevant process conditions. A Dean‐Stark analyzer was used to obtain offline grade and recovery measurements that were used to calibrate the soft sensor. Mean squared errors (MSE) of 62 and 74 were achieved for grade (%) and recovery (%), respectively, and this was obtained using 5‐fold cross validation. The developed soft sensor model has been applied successfully in the real‐time dynamic monitoring of flotation grade and recovery for different grades of ore and operating conditions.

     

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.     

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     

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.     

水基提取技术用于油砂分离的研究进展

油砂作为一种重要的非常规油气资源,其分离技术的研究近些年来引起了国内科研工作人员的重视。介绍了目前世界上最重要的油砂分离技术--水基提取技术的基本原理及影响油砂分离的重要影响因素,阐述了油砂结构、特性与水基提取分离的重要关系及分离条件对沥青回收率的重要影响作用,同时探讨了原子力显微镜用于油砂水基分离过程中相关微观机理研究的重要应用,最后对水基提取技术用于油砂工业生产的流程进行了简单介绍。     

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.     

离子液体促进溶剂萃取油砂沥青

传统水洗法和溶剂萃取法萃取油砂沥青时,存在沥青中含有沙土和残沙中含有油等缺点。为解决上述缺点,本文采用不同比例的乙酸甲酯/正庚烷复合溶剂萃取油砂沥青,研究了离子液体（1-丁基-3-甲基咪唑四氟硼酸盐,[Emim]BF4）对该溶剂萃取体系的萃取率和分离洁净程度的影响。采用红外光谱仪和扫描电镜对萃取后的残沙和沥青的洁净程度进行了定性分析,并结合元素分析仪和电感耦合等离子体发射光谱仪获得萃取后残沙和沥青的洁净程度的定量结果。实验结果表明：当复合溶剂体积比为2∶3时,[Emim]BF4促使沥青回收率达到最大值94.20%,比单纯复合溶剂萃取体系的最大萃取率高7.92%;通过上述测试方法的定性和定量分析,证明了[Emim]BF4能有效解决沥青夹带沙土和残沙中含油的问题。     

Factors Governing Friction Losses in Self‐lubricated Transport of Bitumen Froth: 1. Water Release

Syncrude Canada Ltd. transports bitumen froth, a viscous intermediate product of the oil sand extraction process, 35 km via pipeline. Pipeline transport is feasible because some of the water that occurs naturally in the froth forms a thin lubricating layer around a bitumen‐rich core, thereby greatly reducing friction losses and transportation costs. In this paper, the effect of froth composition (namely, water content) on the formation of the lubricating layer is reported. Tests were conducted with a 25 mm diameter pipe loop and a concentric cylinder froth rheometer. Measurements of pressure gradient and water holdup (free water fraction), along with visual observations, showed that froth containing a lower total water content yielded less free water to the lubricating layer. In the froth rheometer, the conditions for which stable, self‐lubricated flow could be maintained were comparable to those required to maintain self‐lubricated flow in the 25 mm pipe loop.     

Effect of Temperature on the Stability of Froth Formed in the Recycle Process Water of Oil Sands Extraction

The formation of a stable froth on the top of separation vessels plays an important role in bitumen flotation during bitumen recovery from oil sands. The effect of temperature on the stability of froth using recycle process water employed in bitumen extraction was investigated using a water column. The froth became less stable with increasing solution temperature. Once the solution temperature increased above 50°C, irreversible precipitation of the surfactants present in the recycle process water was observed, resulting in a less stable froth.     

Effect of Illite Clay and Divalent Cations on Bitumen Recovery

The adverse effect of illite clay on bitumen recovery was found to be related to its acidity. The addition of calcium or magnesium ions to the flotation deionized water had a marginal effect on bitumen recovery when measured using a Denver flotation cell. However, the co‐addition of illite clay and divalent cations caused a significant reduction in bitumen recovery. The effect was found to be compounded at a lower process temperature and low pH values. Zeta potential distributions of illite suspensions and bitumen emulsions were measured individually and as a mixture to investigate the effect of divalent cations on the interaction between bitumen and illite clay. The presence of 1 mM calcium or magnesium ions in deionized water had a significant effect on the interactions between bitumen and illite clay. Slime coating of illite onto bitumen was not observed in zeta potential distribution measurements performed in alkaline tailings water.     

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.     

Capillary Curves for Ex‐situ Washing of Oil‐Coated Particles

The oil removal efficiency for the ex situ extraction of bitumen from oil sands, or ex situ washing of oil‐contaminated sand and related processes is determined by the balance of forces at the oil/water and solid/fluid interfaces. The objective of this work is to estimate the balance of forces at the interface using dimensionless numbers, and their use in evaluating and engineering ex situ soil washing processes. To this end, bitumen was removed from bitumen‐coated sand particles using a two‐step process. In the first step, the particles were mixed with a suitable solvent (toluene) used, primarily, to reduce the viscosity of bitumen. The particles were then mixed with water or an aqueous surfactant solution capable of producing low interfacial tensions with the solvent‐bitumen mixture. The fraction of oil retained after washing was evaluated as a function of interfacial tension, solvent/bitumen ratio, mixing time, mixing velocity, and particle size. These ex situ washing conditions were normalized using dimensionless film and particle‐based Weber and Capillary numbers. The fraction of oil retained by the particles was plotted against these dimensionless numbers to generate capillary curves similar to those used in enhanced oil recovery. These curves reveal the existence of a critical film‐based Weber number and a particle‐based Capillary number that can be used in the design or evaluation of soil washing processes. The film‐based Weber number also explained literature data that associates interfacial tension with the removal of oil from oil‐based drill cuttings, as well as field observations on the role that particle size plays on the removal of oil in soil washing operations.     

Processibility of Athabasca Oil Sand Using a Laboratory Hyd ro t ransport Extraction System (LHES)

A novel laboratory scale apparatus has been developed and used to assess the extraction performance of oil sands under conditions analogous to current industrial processes. The apparatus can be used to investigate independently, the liberation of bitumen from the sand as well as air‐bitumen attachment and bitumen recovery. Experiments show that lower operating temperatures have a detrimental effect on bitumen recovery and controlled air addition is beneficial for recovery. The liberation of bitumen from sand grains has been found to proceed faster than air attachment and bitumen recovery, making the flotation the ratelimiting step in the extraction process. The potential benefit of staged air injection into hydrotransport pipelines as a possible process aid is discussed.