Fines/Water Interactions and Consequences of the Presence of Degraded Illite on Oil Sands Extractability

The chemical composition of the aqueous phase in oil sand slurries influences bitumen recovery from oil sands, especially those containing greater than 10% fines. The composition is controlled by a combination of mixing and dilution, ion exchange with clay surfaces and precipitation of divalent ions as carbonate minerals. Elevated levels of soluble potassium in the oil sand, which appear to be a marker for degraded illite or smectitic clays, are associated with depressed bitumen recovery. These clays have a swelling character and can contribute divalent ions to the slurry by ion exchange between the clay mineral surfaces and the process water.     

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.     

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.

     

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。     

Water‐Based Bitumen Recovery from Diluent‐Conditioned Oil Sands

Important process development aspects leading to more efficient bitumen recovery from diluent‐conditioned oil sands by water‐based methods are discussed. Bitumen viscosity of 0.5–2 Pa·s is required at the processing temperature and can be reduced to this level by bitumen dilution with an organic solvent. Oil sand porosity, however, poses a restriction on the amount of diluent that can be accepted by the oil sand. Also oil sand‐diluent conditioning time is an important process parameter and can vary from a few minutes for oil sands with low‐viscosity bitumen to several hours if viscosity of the bitumen is high. Additionally, the bitumen separation efficiency during digestion and flotation can be enhanced by reducing the bitumen/water interfacial tension through addition, for example, of tripolyphosphate to the aqueous phase.     

Processibility of athabasca oil sand: Interrelationship between oil sand fine solids,process aids,mechanical energy and oil sand age after mining

Processibility curves have shown that strong inorganic bases or anionic surfactants are effective as process aids in the hot water extraction of bitumen from oil sand, but maximum bitumen recovery for each oil sand type is the same for both types of aid. Nonionic surfactants were not useful and there was no general relationship between recovery and surface tension or pH. Bitumen recovery could be correlated with the fine solids component of oil sand. The amount of NaOH required to reach maximum recovery and the rate of aging of oil sand were also functions of the fine solids content. Shear during slurrying was also found to be important, and it was shown that, without a certain amount of mechanical energy, good bitumen recovery could not be achieved, regardless of how much process aid was used. A theory of processibility is proposed to explain the interactions among process aids, mechanical energy, oil sand fines, and age of oil sand after mining.     

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。     

Clay minerals in nonaqueous extraction of bitumen from Alberta oil sands: Part 1. Nonaqueous extraction procedure

A non-aqueous bitumen extraction process was studied where only toluene and heptane, with no water additions, were used to extract bitumen from two Alberta oil sands ore samples. One sample had a high bitumen (13.5 wt.%) and low fines (5.3 wt.% < 45 μm) contents, while the other sample had an intermediate bitumen (10.5 wt.%) and high fines (23.3 wt.%) contents. Bitumen recovery and product quality were measured under different process conditions such as the ratio of toluene to heptane and settling time. The Dean Stark procedure was used to determine the solids, bitumen and water contents of the extraction products. In addition, the water content was determined by the Karl Fischer titration method. High bitumen recovery was obtained for both oil sands ore samples although the high fines ore sample was more sensitive to the extraction conditions, especially the toluene to heptane ratio. A product with high purity, containing more than 99.5 wt.% bitumen on a solvent-free basis, was produced at room temperature under the optimum extraction conditions tested. The optimum settling time to achieve a pure product was less than 10 min, based on solids and water contents in the supernatant.     

Study of fines in bitumen extracted from oil sands by heat-centrifugation

The temperature dependence of, first, the yield of bitumen extracted from oil sands and, second, of the coextracted solid particles in the bitumen was studied. Centrifugal extractions were performed in an argon (inert) atmosphere at temperatures ranging from 30 °C to 150 °C. The co-extracted solid particles were investigated through digital image analysis, instrumental neutron activation analysis and ash yield. The yield of bitumen increases with extracting temperature and is also dependent on the grade and origin of the oil sand. The quantity of fines, e.g. clay minerals or fine sand particles is dependent on the grade and origin of the oil sand. The total amount of co-extracted solid particles is found to be independent of the extracting temperature.     

Impact of fines content on a warm slurry extraction process using model oilsands

Natural oilsands deposits are composed of a complex mixture of sand, silt, clay, water and bitumen. The bitumen content and silt fraction, or fines (<44 μm), have traditionally been used as primary measures of ore processability. However, it is now known that this rule of thumb is not always applicable. In fact, the variability of oilsands, in terms of both quality and composition, makes it difficult to determine the unbiased effect of any individual component on bitumen extraction from mined ore. To address this problem, a model oilsands (MOS) system has been devised to determine how the interactions of oilsands components affect bitumen recovery. In this preliminary work, the effects of bitumen and fines contents, connate water pH and sodium hydroxide (NaOH) dosages on primary bitumen recovery were determined under the conditions extant in the warm slurry extraction process (WSEP). A three-factor Box-Behnken experimental design was used to quantify the effects. Prior to incorporation into the model oilsands system, each component was characterized to ensure quality control between tests. For the simple model studied in this work, the fines content and sodium hydroxide addition were the most important parameters affecting primary bitumen recovery. Although a small amount of fines was required to recover bitumen in the absence of process aids, an excess of fines was always detrimental to bitumen recovery.     

Preparation of bitumen from oil sand by ultracentrifugation

Ultracentrifugation was investigated as a means to obtain solvent-free bitumen from oil sand. The bitumen from three oil sands of varying grades was separated by placing the sands in specially designed tubes and centrifuging for 2 h at 198 000 at 20 °C. For all grades of oil sand, approximately 70% of the bitumen was recovered. The recovered bitumen was compared to the residual remaining on the sand, and to that extracted by the conventional Soxhlet technique. The ultracentrifuged bitumen contained some emulsified water and a small amount of fine solids. The solvent-extracted material was water-free, but contained a small amount of residual solvent and fine solids. The ultracentrifuge caused some fractionation of the bitumen, resulting in a product slightly enriched in asphaltene components compared to the solvent-extracted material. The residual bitumen remaining on the sand was correspondingly slightly depleted in asphaltenes. However, as evidenced by gas Chromatographic simulated distillation data, ultracentrifugation did retain the light (180–220 °C) components of the bitumen which were lost during the solvent removal step following solvent extraction. Other analyses such as density, viscosity and elemental composition verified that ultracentrifugation resulted in some fractionation of bitumen components.     

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。     

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     

Comparative study of three laboratory methods for the extraction of bitumen from oil sands

Measurements of total organic content and extractable bitumen for a number of different grade oil sands were used to obtain the extraction efficiency of several common bench-scale bitumen recovery techniques. The hot-water process was inefficient for feeds of moderate to high fines content. Soxhlet extraction and spherical agglomeration were found to be of similar efficiency for most grades of feed. For these two processes the efficiency is limited by the mineral fines content, probably because of surface absorption of bitumen components.     

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。     

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.     

Bitumen content estimation of Athabasca oil sand from broad band infrared reflectance spectra

Oil sand is a mixture of quartz grains, clay minerals, bitumen, water, and minor accessory minerals. There is a need in oil sands mining operations for a robust method to estimate total bitumen content in real time; and so modelling of the total bitumen content (TBC) in Athabasca oil sands of Western Canada was undertaken on the basis of hyperspectral reflectance spectra. A selection of different bitumen, water, and clay mineral spectral features (3.0–30.0 µm) was used to develop broad‐band TBC predictive models that have good accuracy, with less than 1.5% error with respect to laboratory methods of bitumen assay. These models are also robust, in that they are independent of mine location. Simple broad band models, based upon previously identified Gaussian features or wavelet features, provide an incremental improvement over the currently deployed industry two‐band ratio model. An improved two‐band model was also developed, which makes use of a combination of the same two bands but normalised to their mean. A wavelet‐based, broad‐band model comprised of indices and five bands, where the bands are normalised to the mean of the bands, adequately addresses the influence of water, clay, and textural variation on selected bitumen features. This five‐band model appears to produce the most robust estimator of TBC, with a dispersion of ∼1.1–1.5%, which can be applied to different sites within a mine and to different mines without additional tuning or calibration, as evidenced by regression slopes of 0.99–1.0 for modelling, validation, and blind data sets.     

Fundamentals of Mechanical Upgrading of Athabasca Oil Sands: Mechanisms of Sand and Bitumen Separation

Abstract

Sand and bitumen were separated mechanically from Athabasca oil sands using cold water in a plate mill. Sand extraction was found to be a function of the product of rotational frequency, oil sands charge weight, and the inverse fourth power of the distance between the rotating plate and the bottom of the mill. Ranges of testing were 20–150 rpm, 10–100 g, and 1.3–27 mm for rotational frequency, oil sand charge, and clearance, respectively. Sand extractions were primarily the result of particle-vessel collisions resulting in brittle failure of the bitumen layer. Extractions reached a limit for each set of experimental conditions after approximately 5 min. The maximum concentration of bitumen in the oil sand fraction was 27% by weight or 50% by volume. A dimensional analysis showed extraction to be a function of Reynolds number, volume fraction of oil sands, and the ratio of clearance to mill radius.     

Bitumen Recovery with Oily Air Bubbles

Air‐kerosene bubbles were used in a novel laboratory scale pipeline loop to assess the extraction performance of poor processing oil sand ores. The addition of kerosene to air, whereby producing oily bubbles, substantially enhanced bitumen recovery from poor processing oil sand ores. The oily bubbles were added in a pipeline loop during bitumen liberation from the sand grains. The bitumen recovery from poor processing ores with the addition of the oily bubbles to the conditioning slurry becomes comparable to that of good processing ores. The present findings can be of substantial benefit to the oil sands industry.     

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