MANAGEMENT OF OIL SANDS TAILINGS

ABSTRACT

In Alberta, oil sands bitumen is utilized for synthetic crude oil (SCO) production by surface mining, bitumen extraction followed by primary (coking) and secondary (catalytic hydrotreating) upgrading processes. SCO is further refined in specially designed or slightly modified conventional refineries into transportation fuels. Oil sands tailings, composed of water, sands, silt, clay and residual bitumen, is produced as a byproduct of the bitumen extraction process. The tailings have poor consolidation and water release characteristics. For twenty years, significant research has been performed to improve the consolidation and water release characteristics of the tailings. Several processes were developed for the management of oil sands tailings, resulting in different recovered water characteristics, consolidation rates and consolidated solid characteristics. These processes may affect the performance of the overall plant operations. Apex Engineering Inc. (AEI) has been developing a process for the same purpose. In this process oil sands tailings are treated with Ca(OH)₂ lime and CO₂ and thickened using a suitable thickener. The combination of chemical treatment and the use of a thickener results in the release of process water in short retention times without accumulation of any ions in the recovered water. This makes it possible to recycle the recovered water, probably after a chemical treatment, as warm as possible, which improves the thermal efficiency of the extraction process. The AEI Process can be applied in many different fashions for the management of different fractions of the tailings effluent, depending on the overall plant operating priorities.     

油砂沥青油的加氢处理研究

油砂沥青油为高密度、高黏度、高金属含量、高残炭的劣质原料,采用沸腾床加氢催化剂,利用反应釜进行加氢处理,考察了反应温度和反应时间对其反应性能的影响,以寻求最佳的沸腾床加氢处理反应条件。实验结果表明,随着反应温度升高、反应时间增加,油砂沥青油的加氢生成油中Fe,Na,Ni,V含量和残炭逐渐降低,最佳反应条件为反应温度430 ℃、反应时间80min,在该条件下,Fe,Na,Ni,V的脱除率分别为99.97%,99.99%,98.11%,99.61%,残炭降低率为72.61%。利用沸腾床进行油砂沥青油的加氢处理,可以有效改善油品性质,满足深加工要求。     

MICROSCOPIC CHARACTERIZATION OF OIL SANDS PROCESSING EMULSIONS

ABSTRACT

Microscopic characterization of oil sands emulsions can be important in the prediction of processing characteristics and process yields in the extraction of oil from oil sands. The size distribution of the emulsion can determine how efficiently the oil can be separated from the water and by what means: mechanically or chemically. In addition, it is possible to characterize the nature of the dispersed phase by using fluorescence behaviour under an optical microscope or via x-ray analysis with a scanning electron microscope. In certain cases it is also possible to characterize the interface between the dispersed and the continuous phases. This paper presents results from our laboratory using microscopic techniques and illustrates their utility, not only for determining the morphology of these economically important emulsions, but also to characterize the composition of the interface itself.     

MICROSCOPIC CHARACTERIZATION OF OIL SANDS PROCESSING EMULSIONS

Microscopic characterization of oil sands emulsions can be important in the prediction of processing characteristics and process yields in the extraction of oil from oil sands. The size distribution of the emulsion can determine how efficiently the oil can be separated from the water and by what means: mechanically or chemically. In addition, it is possible to characterize the nature of the dispersed phase by using fluorescence behaviour under an optical microscope or via x-ray analysis with a scanning electron microscope. In certain cases it is also possible to characterize the interface between the dispersed and the continuous phases. This paper presents results from our laboratory using microscopic techniques and illustrates their utility, not only for determining the morphology of these economically important emulsions, but also to characterize the composition of the interface itself.     

溶剂抽提法处理油砂的研究

用溶剂抽提法对蒙古露头油砂进行处理,实验筛选出了最佳抽提试剂为120号溶剂油,综合考察了抽提温度、剂砂质量比、抽提时间等工艺操作条件对油砂处理的影响。结果表明,在抽提温度75℃、剂砂质量比3：1、抽提时间40min的条件下,120号溶剂油处理油砂可使油提取率达95%以上,回收溶剂油可循环重复利用。该方法经济可行,为油砂的开发利用提供了一条有效途径。     

油泥与油砂尾砂共混萃取回收油泥油的工艺研究

以辽河油田浮渣油泥和玉门油砂萃取后尾砂为研究对象,利用X射线衍射、扫描电镜和梯度筛分表征了其矿物组成、形貌特征和粒径分布。结果表明:尾砂主要含结晶度高的石英、碳酸钙,质地坚实,粒径大于75μm的颗粒占95%以上;油泥主要含黏土矿物,质地松软呈絮状,粒径小于75μm的颗粒占89.7%。根据两者性质上的差异性将其进行合理配比,提出了油泥、油砂尾砂共混萃取的新工艺。通过不同比例油泥与尾砂的共萃取实验,考察了尾砂?油泥质量比、溶剂?(油泥+尾砂)质量比、萃取温度、萃取时间等工艺条件对油泥油收率的影响,确定共混萃取最佳工艺条件为:尾砂?油泥质量比0.5、溶剂?(油泥+尾砂)质量比2、萃取温度60℃、萃取时间20min。在最佳工艺条件下,一级共萃取油泥油收率高达81.8%,二级共萃取油泥油总收率高达89.4%。共混萃取通过利用油砂萃取后尾砂作为萃取助剂,提高了油泥萃取的油分收率,对油泥的无害化和资源化工业生产具有参考价值。     

CHARACTERIZATION OF OIL SANDS MINERAL COMPONENTS AND CLAY-ORGANIC COMPLEXES

ABSTRACT

Differences in oil sands processability and extraction yields can be dependent upon many factors including the composition of the mineral components and the organic complexes that are associated with certain minerals. These mineral-organic associations help provide the bridge which leads to carry over of bitumen with the tailings as well as carry over of water and mineral matter with the product. The nature of the organic component of clay-organic complexes extracted from various streams in an oil sands recovery process is discussed in relation to the stability of both water-in-oil and oil-in-water emulsions formed. These samples have been studied with nuclear magnetic resonance (NMR), scanning electron microscopy (SEM) as veil as with other techniques such as interfacial tension measurements.     

CHARACTERIZATION OF OIL SANDS MINERAL COMPONENTS AND CLAY-ORGANIC COMPLEXES

Differences in oil sands processability and extraction yields can be dependent upon many factors including the composition of the mineral components and the organic complexes that are associated with certain minerals. These mineral-organic associations help provide the bridge which leads to carry over of bitumen with the tailings as well as carry over of water and mineral matter with the product. The nature of the organic component of clay-organic complexes extracted from various streams in an oil sands recovery process is discussed in relation to the stability of both water-in-oil and oil-in-water emulsions formed. These samples have been studied with nuclear magnetic resonance (NMR), scanning electron microscopy (SEM) as veil as with other techniques such as interfacial tension measurements.     

石油羧酸盐表面活性剂在油砂上的静吸附研究

在实验基础上，探讨了石油羧盐表面活性剂在油砂上的静吸附量随液固比、时间、活性剂浓度变化的规律及机理，研究了电解质对吸附等温线的影响，指出了活性在油砂上最大吸附损失的学浓度界限。     

加拿大油砂溶剂提取分离的实验研究

采用半连续溶剂抽提法对加拿大油砂进行了提取分离试验,应用溶解度参数理论以及实验筛选出最佳抽提溶剂为重整汽油。综合考察了提取温度、溶剂流量、提取时间以及提取压力等工艺操作条件对油砂沥青提取的影响。结果表明,在提取温度80 ℃、溶剂流量60 mL/min、提取时间60 min、提取压力1.0 MPa的条件下,油砂沥青提取率达到92.74%。     

炼油企业原油库存在线管理关键方法研究

炼油企业是典型的流程工业.为支持生产计划、调度和采购等生产经营活动,要对原油库存进行在线管理.这要求原油库存管理系统能提供"任意时刻"的原油库存状态.介绍基于离散事件动态系统理论提出的一种有效的方法,通过这个方法,只需记录指定的时间与事件点的库存信息.这些信息再经过简单的数学计算可获得计划期内任意时刻的库存状态.同时在生产经营过程中,通过现场总线技术实时采集指定的时间和事件点各储油设备的实际库存,随着计划的进行不断修正生产计划与调度仿真系统的模拟库存量,提高了仿真系统库存信息的准确性.这一方法是基于Window环境下实现的,并已应用于某炼油厂.     

13NMR CHARACTERIZATION OF HUMIC MATTER PRESENT IN DIFFERENT OIL SANDS

ABSTRACT

Insoluble organic matter (humic matter) present in oil sands can alter the wettability of the inorganic matrix and thereby cause serious problems during bitumen recovery.

Using a cold water agitation test, solids rich in organic matter were isolated from various oil sands which were chosen to reflect different behavior in the hot water extraction process.¹³C NMR examination of these separated solids showed significant structural variations between samples isolated from different oil sands. Humic matter from Utah oil sand appeared to be more aliphatic than that derived from Athabasca oil sand.

Humic acids extracted from organic rich solids as a result of prolonged treatment with 2% NaOH show remarkable similarity in their ¹³C NMR spectra. Humins differ substantially in the relative contribution of the terrestrial and marine source material. There was apparent correspondence between poor bitumen separation and the presence of humin with highly paraffinic structures.     

13NMR CHARACTERIZATION OF HUMIC MATTER PRESENT IN DIFFERENT OIL SANDS

Insoluble organic matter (humic matter) present in oil sands can alter the wettability of the inorganic matrix and thereby cause serious problems during bitumen recovery.

Using a cold water agitation test, solids rich in organic matter were isolated from various oil sands which were chosen to reflect different behavior in the hot water extraction process.¹³C NMR examination of these separated solids showed significant structural variations between samples isolated from different oil sands. Humic matter from Utah oil sand appeared to be more aliphatic than that derived from Athabasca oil sand.

Humic acids extracted from organic rich solids as a result of prolonged treatment with 2% NaOH show remarkable similarity in their ¹³C NMR spectra. Humins differ substantially in the relative contribution of the terrestrial and marine source material. There was apparent correspondence between poor bitumen separation and the presence of humin with highly paraffinic structures.     

准噶尔盆地西北缘红山嘴油砂特征

准噶尔盆地西北缘红山嘴油砂特征研究对于指导该区油砂的进一步勘探开发有着重要的意义。为此，采用物理和地球化学实验的方法，研究了准噶尔盆地西北缘红山嘴地区油砂的物理特征和油砂含油率特征，初步计算出了该区油砂油的地质资源量：通过含油率法得出该区0～50 m埋深范围内的油砂储量为3 200×10⁴t，50～100 m埋深范围内的油砂储量为2 700×10⁴t；然后采用生物标志物的方法探讨了该区油砂油的生物降解程度。结果认为：该区油砂油降解程度普遍很高，基本都在8级以上。     

江油厚坝油砂岩成藏条件分析

厚坝单斜构造的构造位置，处于龙门山北段推覆体构造带内，归属于前龙门山推覆体构造带的断层隐伏前锋构造带内。通过研究分析，江油厚坝油砂岩具备了成藏的条件。①油源大量存在且丰富，震旦系烃源岩是龙门山北段优质的烃源岩，厚坝油砂岩的油源来自于震旦系；②侏罗系沙溪庙组油砂岩良好的储集条件，为油气的聚集提供了储集空间。油砂岩储层的主要孔隙类型是粒间溶孔、粒内溶孔；③喜山期重新活动的印支期出露前锋和晚期高角度断裂为震旦系烃源岩提供了运移通道。二郎庙断裂带是邻接厚坝油砂岩的唯一断裂构造。喜山期的高角度断层和开启性裂缝，是构成厚坝油砂岩与深部断裂带之间油气运移通道；④油气的运移、聚集时间与古隆起的形成及构造多期次活动时期相匹配，形成厚坝油砂岩喜山期的独特成藏模式。     

HYDROPROCESSING OF DISTILLATES DERIVED FROM OIL SANDS AND COAL: SUMMARY OF CANMET FINDINGS

ABSTRACT

The development of technologies for refining commercially available synthetic crudes from Alberta oil sands is of increasing economic importance in view of projected expansions in their utilization. Similar developmental concerns will arise in upgrading refinery residual oils and possible use of coal-derived liquids. Extensive information is now available on the effectiveness of hydroprocessing technology in upgrading middle distillates from oil sands and light and middle distillates from coal. Although standard refinery processes are inadequate for production of specification diesel and jet fuels from these unconventional sources, it appears that major improvement is attainable when different catalytic systems are applied. Experimental findings which address relevant phenomena are reviewed and new directions in technology development are identified.     

HYDROPROCESSING OF DISTILLATES DERIVED FROM OIL SANDS AND COAL: SUMMARY OF CANMET FINDINGS

The development of technologies for refining commercially available synthetic crudes from Alberta oil sands is of increasing economic importance in view of projected expansions in their utilization. Similar developmental concerns will arise in upgrading refinery residual oils and possible use of coal-derived liquids. Extensive information is now available on the effectiveness of hydroprocessing technology in upgrading middle distillates from oil sands and light and middle distillates from coal. Although standard refinery processes are inadequate for production of specification diesel and jet fuels from these unconventional sources, it appears that major improvement is attainable when different catalytic systems are applied. Experimental findings which address relevant phenomena are reviewed and new directions in technology development are identified.     

风城地区油砂层分布规律及其控制因素

风城油砂矿位于新疆准噶尔盆地西北缘克拉玛依市乌尔禾镇北北东方向12 km处,是我国目前发现的最大的油砂矿。通过对该地区地层资料的统计及分析,并对白垩系进行了地层对比,将该区白垩系划分成了4个沉积时期,并对4个时期的油砂层进行了对比;同时还分析了侏罗系砂岩及油砂的分布特征,得出了油气主要沿断层和不整合面运移,并随运移距离的增加,油砂含油率降低的认识。通过研究初步掌握了该区油砂的分布规律及其控制因素。     

奇数碳烷基间二甲苯磺酸钠在大庆油砂上的吸附

 摘要：考察了11种结构明确的奇数碳烷基间二甲苯磺酸钠(mCn-hS)在大庆油砂上的吸附,探讨了mCn-hS的初始质量浓度、分子结构、分子中烷基链长度及助剂对其吸附量的影响。结果表明,随着mCn-hS初始质量浓度的增大,其在大庆油砂上的吸附量先增大至饱和,后略有降低;烷基链长度相同的mCn-hS,随着其中芳基位置向烷基链中间位置移动,其在大庆油砂上的吸附量降低;NaCl和NaOH的加入使mCn-hS在大庆油砂上的吸附量增大,而异戊醇的加入使其降低;加入助剂后,随着mCn-hS分子中烷基链长度的增加,mCn-hS在大庆油砂上的吸附量减小。     

CHARACTERIZATION OF SOLVENT-INSOLUBLE ORGANIC MATTER ASSOCIATED WITH MINERAL MATTER FROM OIL SANDS*

Considerable quantities of insoluble organic matter (IOM) are known to be associated with certain solid fractions found in oil sands. This organic matter is believed to be partly responsible for the intractability of the sludge generated by the hot water process used for the extraction of bitumen from Alberta oil sands. In previous investigations we had attempted to enrich the insoluble organic matter by dissolving the minerals in concentrated HCl/HF mixtures. As a result of this severe acid treatment the inorganic material is decomposed, but the organic constituents are also likely to undergo significant changes. In the present work we have used a milder HCl/HF treatment for mineral dissolution. The results from the current investigation are compared with the results of the previous study to assess the chemical alterations of the organic matter resulting from the two treatments.

The fractions obtained from the mild acid treatment were analyzed using solid state ¹³C NMR spectroscopy and elemental analysis. Latter results have been discussed in terms of a van Krevelen diagram which is derived by plotting the atomic H/C ratios against O/C. The NMR data were used to calculate the aromaticities of the various organic fractions. Based on the elemental compositions and the NMR data, it is suggested that the IOM associated with the sludge solids is derived from terrestrial sources.