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.     

Effect of clays and calcium ions on bitumen extraction from athabasca oil sands using flotation

A novel approach, based on the doping of rich estuarine oil sands with calcium and/or clays, was developed to study bitumen extraction. The batch flotation tests showed that the addition of either calcium ions up to 40 p.p.m., or kaolinite, illite and montmorillonite clays at 1 wt% of oil sands processed had marginal effect on bitumen recovery from the estuarine ores. A sharp reduction in bitumen recovery was observed only when calcium ions greater than 30 p.p.m. and 1 wt% montmorillonite clays were added together. While bitumen recovery correlated well with changes in water/air/bitumen contact angle, no correlation was found between bitumen recovery and measured zeta potential of clays or surface tension of the supernatants from the flotation slurry. The wettability of bitumen was identified as a key element in determining bitumen recovery. The aqueous solution analysis for calcium ions showed that most of the added calcium ions disappeared from the solution when montmorillonite clays were present. The addition of illite or kaolinite clays changed the calcium ion concentration in the slurry only marginally. Stronger adsorption of calcium ions on montmorillonite than on either kaolinite or illite is considered to be responsible for the increased bitumen wettability, and hence reduced bitumen recovery.     

不同有机溶剂对新疆油砂沥青的组成性质影响

油砂作为一种非常规石油资源,越来越受到人们的重视。油砂沥青的含量和性质对其开发有着重要的影响。有机溶剂抽提可以测定油砂沥青的含量。本文研究了3种溶剂对新疆油砂的抽提能力,并对不同溶剂抽提得到的新疆油砂沥青进行了性质分析。结果表明,新疆油砂含油率（甲苯测）为11.75%,属于中品位油砂矿;甲苯、氯仿和石油醚3种不同溶剂对新疆油砂沥青进行抽提,发现3种溶剂抽提能力的大小关系为氯仿＞甲苯＞石油醚;抽提过程中,氯仿表现出对胶质和沥青质较强的萃取能力,而石油醚对沥青质的萃取能力几乎为0,采用氯仿可以更准确地测定油砂沥青的含量。氯仿抽提得到新疆油砂沥青及其组分的杂原子含量和分子量高于甲苯和石油醚抽提的。由红外谱图发现,氯仿抽提得到的油砂沥青的含氧、含硫官能团的吸收峰强度大于甲苯和石油醚抽提的,表明氯仿对油砂沥青中极性物质的抽提能力更强。     

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.     

Understanding bitumen partial upgrading through process modelling and simulation

Partial upgrading is an emerging direction in the processing of Canadian oil sands bitumen in response to the economic and environmental challenges in the oil sands industry. Partial upgrading aims to improve bitumen quality only to the level at which pipeline specifications are met without use of diluent. Given that partial upgrading technologies have not yet reached commercial deployment, there is a lack of technical data to assess the expected benefits in terms of energy input and greenhouse gas emissions reduction. In this study, we present an assessment of a partial upgrading scheme using detailed process simulation. We developed a conceptual process scheme considering visbreaking, solvent deasphalting, and naphtha hydrotreating as the core partial upgrading processes. Reactor models were assembled using experimental data from CanmetENERGY's pilot plant facilities and from the literature and integrated into a plant‐wide simulation model. Simulations allowed the examination of trends in partial upgrader product yields and quality and enabled a comparison with traditional bitumen upgrading.     

Thermo‐physical properties of n‐pentane/bitumen and n‐hexane/bitumen mixture systems

The gravity drainage as a result of viscosity reduction is the main governing mechanism of the solvent‐aided thermal bitumen recovery processes. Therefore, the density and viscosity of the diluted or heated bitumen are essential to predict the oil production rate. In this paper, we report thermo‐physical properties of n‐pentane/bitumen and n‐hexane/bitumen mixtures. The density and viscosity of Athabasca bitumen diluted with n‐pentane and n‐hexane were measured at different temperatures (30 to 190 °C), pressures (2 to 8 MPa), and solvent mass fractions (0.05 to 0.5). Various correlations and mixing rules proposed in the literature were examined to calculate the density and viscosity of the diluted bitumen. This study proposes appropriate mixing rules and generalized parameters for predicting the density and viscosity of solvent‐bitumen systems. Our findings will find applications in the design and simulation of heavy oil and bitumen solvent‐aided thermal recovery processes.     

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.     

Rheological properties of bitumen in water emulsions with added solids

Experimental work was carried out to investigate the rheological properties of bitumen in water emulsions containing solids of different shape and size. The bitumen volumetric concentration was varied up to 60%, solids free basis, and the solids volume fraction (total volume basis) was varied up to 0.2. Irregular-shaped silica sand (average diameter: 9 and 33 μm) and smooth spherical glass beads (average diameter: 27 and 44 μm) were used as the added solids. In the low shear stress range, shear thinning behavior was observed for bitumen in water emulsions. At high shear stress, the viscosity of the emulsions became fairly independent of the shear stress. The addition of solids to the bitumen emulsions increased the mixture viscosity. The addition of irregular-shaped silica sand gave a higher viscosity than a similar addition of the spherical glass beads. The viscosity of the emulsion/solids mixtures was influenced by the solids size as well; the smaller size particles gave a higher viscosity. The addition of solids to the bitumen emulsions also induced shear thickening (dilatancy) behavior at high solids volume fraction. The degree of the shear thickening increased with the oil concentration.     

有机溶剂萃取加拿大油砂应用研究

介绍了溶剂作为萃取剂分离油砂的技术,溶剂萃取油砂过程包含两个阶段:沥青相向溶剂的溶解过程和沥青、溶剂与砂粒的分离过程。考察了单一溶剂甲苯、丙酮、乙酸乙酯和甲苯/正庚烷、丙酮/正庚烷、乙酸乙酯/正庚烷组成的复合溶剂体系在相同条件下对油砂沥青的萃取率,在此基础上进一步对比了不同溶剂体系对沥青四组分饱和分、芳香分、胶质和沥青质的萃取效果,同时考察了不同浓度的沥青-溶剂溶液的表面张力,结果表明在油砂萃取过程中沥青-溶剂体系的表面张力主要取决于所选溶剂的种类,而沥青的浓度对溶液表面张力的影响不大。混合溶剂体系甲苯/正庚烷、丙酮/正庚烷、乙酸乙酯/正庚烷相比纯溶剂萃取率较高,其沥青溶液表面张力较低,是良好的分离油砂溶剂体系。     

In situ upgrading of bitumen and heavy oils via nanocatalysis

Thermal in situ bitumen production has introduced a different engineering approach compared to conventional oil exploitation. Steam injection for example, allows the development of a relatively confined liquid and gas chamber surrounding and along the length of the production wells. This heated place can be converted into a reactor for upgrading processes founding expectations of extensive reservoir upgrading of unconventional oils reducing the total energy currently required to both exploit the reservoir and surface upgrade the produced bitumen. These could also selectively transform contaminants into harmless products remaining in the reservoir. This article highlights the nanocatalytic in situ upgrading paths that may result in economical and environmentally efficient oil sands exploitation. © 2012 Canadian Society for Chemical Engineering     

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。     

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.     

加拿大油砂沥青部分改质技术综述

介绍了加拿大油砂资源情况、主要性质、改质技术现状和原油外输能力,重点调研了有工业应用潜力的部分改质技术,包括工艺技术现状、核心流程、技术特点和存在问题等。从部分改质产品性质、改质深度、改质过程的碳排放强度、是否存在副产品等多种维度,分析油砂沥青部分改质技术的未来发展趋势。其中对油砂沥青进行缓和热裂解,或缓和热裂解结合沥青质脱除技术是油砂沥青部分改质的技术核心;目标是在满足加拿大管道要求的前提下,尽可能减少稀释剂用量、保证部分改质产品的稳定性,降低改质工艺过程的碳排放强度。     

油砂沥青质对油砂沥青中甲苯残留的影响

利用热重质谱联用仪（TG-MS）分析了三种油砂沥青（印尼油砂沥青、伊朗油砂沥青、加拿大油砂沥青）中的甲苯残留以及油砂沥青质含量对油砂沥青中甲苯残留的影响,并在此基础上,进一步研究了油砂沥青质中的甲苯残留。结果发现,不同油砂沥青中甲苯残留量存在一定差异,其中印尼油砂沥青中的甲苯残留量最多。进一步对沥青质质量分数分别为10%、19%、30%的油砂沥青样品进行热重质谱实验,发现随着油砂沥青中沥青质含量的增加,甲苯的残留量会成倍增加。以加拿大油砂沥青质为例,研究了油砂沥青质对溶剂残留的影响,发现油砂沥青质具有对甲苯分子的夹带能力,导致甲苯分子在超过自身沸点40℃以上才能从沥青质中分离出来。油砂沥青中其他组分的存在也会加剧沥青质对甲苯的夹带作用。此外,研究还发现,在350~650℃时,油砂沥青质可以热解产生甲苯,而且油砂沥青中的沥青质含量越高,热解生成的甲苯越多。     

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.     

N.m.r. line shape-relaxation correlation analysis of bitumen and oil sands

The first results of the analysis of bitumen and oil sands using the recently developed n.m.r. spingrouping technique are presented. The n.m.r. relaxation experiments were carried out on bitumen, and on natural and dried oil sands samples. The results indicate that the spin-grouping can resolve and quantify several components of the samples studied. The bitumen and bitumen fraction of the oil sands are resolved according to their spin-spin relaxation times into three major groups: solid-like (rigid), solid-like (mobile) and semi-liquid. The water in the oil sands exists in two different environments. Tentatively one environment is assigned to be the bridges between the sand grains, while the other is assigned to be the clay surface. One can conclude that with spin grouping of complex mixtures the decomposition (in which components are resolved according to their dynamic state) is possible. The accuracy of such resolution is of the order of a few per cent.     

Interaction between Bitumen and Fines in Oil Sands Extraction System: Implication to Bitumen Recovery

Colloidal interactions between bitumen and fines, extracted directly from oil sand ores, were investigated with zeta potential distribution measurement and surface force measurement using an atomic force microscope (AFM). Fines from good processing ores exhibit a negligible attachment to bitumen surfaces, due to hydrophilic nature of the fines. Fines from poor processing ores exhibit a stronger attachment to bitumen surfaces by an attractive hydrophobic force between bitumen and fines, due to hydrophobic nature of the fines and the presence of high concentration divalent cations in the processing water.