Glow discharge excited low temperature ashing: A new technique for separating mineral matter of coals

Low temperature ashing techniques are widely used to determine mineral matter content and in the analysis of the composition of the inorganic matter in coal and coal products. This Paper presents a new technique which makes it possible to ash coals in 4 (low-rank coals) to ≈8 (high-rank coals) h per gramme. The problem of the formation of LTA artefacts is described and differences between authigenic and artefactic minerals are indicated.     

Isolation and characterization of various types of organic matter in oil sands tailings sludge

In bitumen extraction of oil sands by hot water, the problem of sludge accumulation is, at least partially, attributable to the presence of unrecovered bitumen as well as acetone solubles and so called ‘insoluble organic matter’ (IOM) on the surfaces of inorganic particles. A comparative study of the bitumens separated from both sludge and the original oil sands feed suggested that the former was depleted in high molecular weight fractions. Examination of the organic matter extracted from sludge with acetone indicated that asphaltene constituents, as well as long chain fatty acids, could report with the acetone solubles. The structural parameters of the IOM derived from sludge were, in general, similar to those for oil sand IOM.     

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.     

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.     

提高有机碳氧化温度快速测定有机-无机复混肥料中有机质的含量

为了缩短分析时间,利用电热恒温油浴锅代替水浴锅,将有机一无机复混肥中的有机碳在重铬酸钾一硫酸溶液中的氧化温度提高到170～180℃,能在5～10min内完全将有机碳氧化,比用沸水浴加热氧化的时间缩短2／3,氧化更完全,方法的准确度、精密度更高。     

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.     

A novel dissolution-precipitation method for high-efficiency separation of oil-wetted oil sands

Dissolution-precipitation is a novel high-efficiency method for separating oil-wetted oil sands. Four dissolving agents and three precipitating agents were studied to select the optimal combination. Results showed that N,N-dimethylcyclohexylamine (DMCHA) and methanol were the optimal dissolving and precipitating agents, respectively. The chemical group compositions, element content, and H/C atom ratio of bitumen separated by DMCHA-methanol were analyzed, and the optimal conditions for oil sands separation were determined, under which the bitumen recovery reached 96.4%. After six separation cycles with DMCHA-methanol, the bitumen recovery remained above 93%.     

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。     

油页岩低温干馏过程的Aspen Plus模拟

利用Aspen Plus系统流程模拟软件模拟油页岩的低温干馏,并按照含油率测定实验工况来设置系统流程,以探讨将Aspen Plus应用于油页岩热解领域的可行性。针对吉林地区桦甸一矿4层和二矿11层的油页岩试样进行模拟,并将所得的含油率、含水率、半焦产率、干馏气体产率及半焦中各元素含量等模拟数据与实验值进行对比分析,模拟结果与实测值间的误差均控制在合理范围之内。对比结果表明,系统流程的建模及物性参数设置是正确合理的,可为后期构建完整的油页岩综合利用系统提供参考。     

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.     

Gasification kinetics of oil sands coke

Kinetics of steam gasification of delayed and fluid cokes derived from Athabasca bitumen have been studied in 6.35 cm diameter stirred and fixed bed reactors. Experiments were carried out at atmospheric pressure and at temperatures between 800°C and 930°C. The coke particle size ranged from 0.1 to 3.5 mm, and the steam partial pressure was varied from 15.2 to 60.6 kPa. Scanning electron microscopy, surface area analysis, and mercury porosimetry were employed to relate physical structure changes in the solids to experimental kinetic data. Several kinetic models for gasification were tested with the experimental gasification data. Rate expressions are presented for carbon conversion and for the release of sulphur.     

Upgrading of middle distillate fractions of a syncrude from Athabasca oil sands

Current processes for upgrading bitumen from Athabasca oil sands produce synthetic crudes which are high in aromatics and deficient in hydrogen. As a consequence, middle distillate fractions derived from these syncrudes produce diesel fuels of low cetane number and jet fuels which are hydrogen deficient. Results obtained from bench-scale hydrotreating experiments indicate that quality fuels may be produced from Athabasca syncrudes. Middle distillate fractions from this source were subjected to high-severity hydroprocessing in a continuous-flow reactor unit using conventional hydrotreating catalysts which were pre-sulphided by a mixture of $\text{H}{}_2\text{H}{}_2\text{S}$. Aromatic hydrogenation at high temperatures and pressures was affected by the approach to thermodynamic equilibrium, however, at lower temperatures, in some cases virtually 100% saturation was achieved and treated fractions were found to meet cetane number and jet fuel smoke point requirements. Data treatment in the present study includes a model for the hydrogenation kinetics and correlations between aromatic carbon and fuel combustion properties.     

Recovery,characterization and conceptual modelling of Non-Bituminous organic materials from oil sands

The hot water process has recovered approximately 90% of the bitumen in oil sands, but the remaining 10% of bitumen and naphtha has been lost to the tailings pond. Recovery of bitumen and non-bituminous combustibles (NBC) from centrifuge, scroll and final tailings has been considered. The effects of four sequestering agents, and of chemical additives such as CaCl₂ and FeCl₃ on the flotation behavior of bitumen, NBC and minerals in these tailings have been investigated. A simple method of isolating NBC materials has been developed. The flotation of both bitumen and NBC was enhanced by phosphate treatment and depressed by EDTA. NBC was characterized by its physical properties, energy content, functionality and chemical analysis. A conceptual model explains the interactions between the bitumen, minerals and NBC fractions present in tailings slurries.     

High-efficiency separation of oil sands using ChCl-based deep eutectic solvents

Deep eutectic solvents (DESs) are a kind of potential lixiviant for extraction processing. Unlike conventional ionic liquids (ILs), DESs are relatively cheap and environmentally friendly. Herein, three different ChCl-based DESs, namely, choline chloride/urea, choline chloride/ethylene glycol, as well as choline chloride/propandioic acid, were synthesized and used to enhance bitumen recovery from oil sand by petroleum ether extraction. The results showed a multiphase system formed after mixing the components at ~25°C, consisting of sands and clays, a DES layer, and a petroleum ether layer containing the bitumen. These DESs were immiscible with bitumen or petroleum ether. Coupled with a density difference, a clear phase separation was presented between the bitumen–petroleum ether mixture and DES. The DES functioned as a separating agent, keeping the petroleum ether–bitumen mixture and spent sand apart from each other. The results showed that the bitumen recovery was increased by ~12% compared with that without the DESs. We deduced that the enhancement in the separation may result from the reduction of adhesion between bitumen and sand by the DESs. The ChCl-based DESs and petroleum ether could be readily recycled to reduce industrial costs. After 10 cycles, the bitumen recovery remained above 86%.     

Some chemistry of organosulphur compound types occurring in heavy oil sands: 2. Influence of pH on the high temperature hydrolysis of tetrahydrothiophene and thiophene

The hydrolysis of thiophene at high temperatures and pressures has been examined in relation to the steam-stimulated recovery of high-sulphur tar sands and heavy oils. The influence of pH has been examined in the hydrolysis of both thiophene and tetrahydrothiophene considered to be reasonable models for organosulphur molecular types in heavy oils. Mechanisms are proposed to account for the products observed under acidic, neutral and basic conditions.     

Thermophysical characterization of oil sands. 2. Acoustic properties

Propagation characteristics of shear (S) and compressional (P) waves are investigated for oil sands from the Athabasca, P.R. Spring, N.W. Asphalt Ridge and Circle Cliffs deposits. These studies are oriented towards applications of acoustic techniques in characterization, diagnostics and control of in-situ extraction methods currently envisaged for oil sand bitumen. The magnitude of the temperature dependence of S and P wave velocities is directly related to the bitumen content of the oil sand. The origin of the pronounced changes in Sand P wave velocities (or travel times) in the temperature regions 24–200 °C and 425–500 °C is traced to the thermal decomposition of oil and sand bitumen. The S and P wave velocities generally decrease with increasing bitumen content. Other variables that are studied, such as moisture content and bulk density, have relatively minor effects on the magnitude of the measured S and P wave velocities.