水辅助溶剂法提取油砂中的沥青

开发了一种水辅助溶剂法从油砂中提取沥青的技术。该方法通过在油砂固相与有机溶剂间介入水层提取油砂中的沥青。以内蒙古扎赉特旗油砂矿为研究对象,考察了温度、剂砂质量比、提取时间、甲苯在复合溶剂中的含量及溶剂的种类与性质对沥青回收率高低的影响,结果表明：最佳提取条件为提取温度50℃,剂砂质量比1∶1,提取时间25min。沥青回收率与提取溶剂的性质紧密相关,水层介入有效降低了固体微粒组分在有机相中的含量,且便于后续的有机相与泥砂相的分离。通过对各种溶剂提取的沥青进行组分分析,发现各种溶剂对沥青提取能力的差异性源于溶剂的化学组成和结构不同。本文相关研究结果对溶剂法提取油砂中沥青技术及溶剂种类的选择具有指导作用。     

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.     

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。     

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.     

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.     

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。     

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.

     

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.     

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。     

Removal of intractable fine solids from bitumen solutions obtained by solvent extraction of oil sands

During solvent extraction of bitumen from oil sands, the bitumen solutions produced are usually contaminated with fine solids. The water-wettable fines may be eliminated by utilizing simple solids agglomeration techniques during extraction. Intractable oil-wetted solids can also be removed by chemical treatment to improve settling rates, allowing separation without the need for centrifugation. Some data from small-scale batch and continuous experiments are presented to illustrate the techniques employed.     

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.     

克拉玛依油砂溶剂萃取分离实验研究

以克拉玛依油砂为实验对象,考察石油醚、环己烷、正戊烷、正庚烷、甲苯、CS2及复合溶剂EOSA萃取分离油砂沥青的效果,确定EOSA为最佳萃取溶剂。研究了温度、溶剂用量、时间对EOSA萃取分离油砂沥青收率的影响。结果表明,在萃取温度30℃、剂砂比2 mL/g条件下萃取30 min,油砂沥青的收率可达95%以上。再生实验结果表明,在60~80℃条件下,溶剂回收率超过99%。该工艺具有无水参与、零排放、低能耗、高收率等优点。     

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.     

Kinetics of bitumen extraction from oil sands using organic solvents

The kinetic study of bitumen extraction from oil sands is significant for efficiency improvement and reactor design in industrial applications. Here, an improved pseudo-first-order kinetic model was established with the assumption of a constant Sherwood number, which took into account the mass transfer area. Five organic solvents were used for the extraction kinetics of the prepared bitumen microbeads. The improved pseudo-first-order kinetic model exhibited excellent fitting effects. Petroleum ether/dichloromethane was proved to be the best solvent. The results also showed an exponential decrease in the diameter of the bitumen microbeads and a linear increase in mass transfer coefficients with time for all the solvents. The kinetics of bitumen extraction from oil sands using different solvents were predicted according to the corresponding average mass transfer coefficients. The experimental results confirmed that the improved kinetic model was capable of describing the mass transfer process of bitumen extraction from oil sands.     

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.     

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.     

阳离子聚丙烯酰胺辅助溶剂萃取油砂沥青工艺研究

使用甲苯、正庚烷、石油醚和石脑油,辅以阳离子聚丙烯酰胺和离子液体等助剂对加拿大亲水型油砂进行了萃取实验,并从沥青回收率、沥青中细沙夹带和残砂形貌3个角度对沥青分离效果进行了分析评价,最终认为阳离子聚丙烯辅助石脑油萃取油砂沥青是一种经济可行的工艺路线。随后文章从助剂浓度、助剂存放时间、助剂和油砂比例、溶剂和油砂比例等角度出发,对工艺参数进行了优化。结果表明,在室温条件下,当石脑油：0.05% CPAM水溶液：油砂为3：2：1时,沥青回收率由72.29%提升至78.29%。此外,通过对沥青的红外分析和残砂的扫描电镜分析还发现,阳离子聚丙烯酰胺在甲苯和石脑油萃取体系中均有夹带减小细砂的功效。     

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.     

Parameters and mechanisms in the solvent extraction of mined athabasca oil sand

The efficiency of solvent extraction of bitumen from mined Athabasca oil sands has been studied in laboratory-scale, batch, stirred vessels. Solvent type, solids concentration, stirrer speed and contact time have been identified as important parameters. A theoretical analysis of the extraction process provides a basis by which the various parameters are assessed in terms of relative overall mass transfer coefficients. However, because the size distribution of the oil sand aggregates is difficult to reproduce, the analysis is limited. Greater reproducibility, and similar quantitative results were obtained for the dissolution of pure bitumen from the bottom of the stirred vessels. It is shown that highly aromatic solvents such as benzene and toluene can dissolve bitumen 3–5 times faster than an essentially alpha tic solvent such as kerosene. There is evidence, however, which indicates that solvent properties other than aromaticity are also important. The data indicate that a minimum stirrer speed must be exceeded before the extraction of oil sand or pure bitumen will proceed at a reasonable rate. Above this minimum rate, the mass transfer coefficient increases linearly with stirrer speed. The solids concentration is also important since the data suggest that a higher efficiency is obtained at higher solids concentrations in the range of solid loadings studied.     

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.