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。     

用油砂沥青制备水性沥青涂料的研究

为开发油砂沥青涂料的制备工艺，对油砂沥青在水性涂料中的应用技术进行了探索。首先测定了沥青样品的基本性质，进一步考察了乳化沥青的制备工艺，在此基础上针对丙烯酸乳液与乳化沥青配比、体质填料用量、油砂沥青替代量对涂料涂层性能的影响等方面对水性沥青涂料的制备过程进行了研究。研究结果表明：油砂沥青的沥青质含量高于 90#标准石油沥青，在乳化过程中通过加入活性剂十六烷基三甲基氯化铵（ 1631）、稳定剂氯化钙来辅助牛脂基丙撑二胺（ DAT）乳化的方式，可得到筛上剩余量和蒸发残留量符合行业标准要求的乳化沥青。在 m（水性丙烯酸乳液） ∶m（乳化沥青） =1∶1的配比下，加入 m（硫酸钡） ∶m（滑石粉） =1∶1的体质填料 35 g，油砂沥青的替代量达到 80%条件下，能制得较好粘附性能和一定防腐性能的水性油砂沥青涂料。     

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。     

印尼特细油砂的基本性质和加工路线研究

印尼特细油砂是一种原产于印度尼西亚的稠油资源,常见有黄色和黑色两种。通过甲苯溶剂抽提法和减压蒸馏法可得到油砂沥青和细砂粒,得到的油砂沥青和砂粒用于油砂基本性质的测定。并简单探讨了该油砂适宜的加工路线。印尼油砂具有含油率高,含硫量高的特点,并且适合采用热解法进行后续加工成轻质油。     

基于固体13C核磁共振技术对油砂沥青质结构的研究

采用固体13C核磁共振(13C NMR)技术对油砂沥青质的化学结构特征进行详细的研究。通过对油砂沥青质的核磁谱图分析,获得了表征油砂沥青质结构特征的12个碳结构骨架参数。根据研究分析结果,油砂沥青质中的脂碳含量达60%左右,表明其化学结构主要以脂碳结构为主。在脂碳中,亚甲基含量最多,主要出现在脂肪链中,且其脂肪链平均长度小于8个碳原子,可推断为中等长度脂链;芳香碳含量小于40%,其中质子化芳香碳含量多于非质子化芳香碳。在非质子化芳香碳中芳香桥碳含量最多,可推断芳香碳呈多环模式;羰基碳在油砂沥青质结构中所占比例极小。虽然基于获得的油砂沥青质的元素组成,可以将油砂沥青质归类到Ⅰ型干酪根,但是两者在成烃潜量和结构特征都存在较大差异,由此判断油砂沥青质并非干酪根的降解产物。     

油砂沥青质分离纯化及其热裂解研究

为更好地开采并利用油砂,以新疆某油田油砂沥青质为研究对象,在分离纯化后进行热裂解实验研究,探寻油砂沥青质的转化规律。实验结果表明,超声震荡可以快速将沥青质包裹组分释放出来,缩短沥青质的分离纯化时间;沥青质中3种重要物质生烃、生气、生焦含量变化与温度和时间的关系非常密切;沥青质裂解具有明显的一级反应动力学特征,随着温度的升高,时间逐渐缩短,而其表观速率常数总体呈增加的趋势。     

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。     

油砂沥青水溶液与溶剂抽提及分离

采用热碱水法对内蒙油砂进行了沥青抽提及分离实验,并对产物沥青进行了性质分析.实验表明,热碱水抽提适宜条件为:碱浓度0.25%、反应温度95℃、搅拌速度80r·min-1、固液比S/L=1:1.5、反应时间15min,沥青收率可达92%.本研究为油砂资源的研究和开发利用提供了理论和基础实验参数.     

咪唑类离子液体辅助溶剂萃取油砂沥青研究

采用阴离子为BF₄^-,阳离子为1-烷基-3-甲基咪唑类的离子液体（Ionic Liquids,ILs）辅助丙酮/正庚烷复合溶剂和甲苯2种溶剂萃取加拿大油砂中的沥青,考察了ILs辅助2种溶剂萃取油砂沥青过程中,ILs阳离子咪唑环一取代位上的碳链长度对沥青萃取率和固体夹带的影响。实验结果表明,随着ILs阳离子咪唑环一取代位上碳链的增长,沥青的萃取率总体逐渐降低。碳链从甲基变化到正己基,在丙酮/正庚烷复合溶剂体系中,沥青萃取率由9.29%降到8.55%;在甲苯体系中,沥青萃取率由10.05%降低到9.45%。但在2种体系中,加入碳链为正丁基的IL的沥青萃取率高于碳链为正丙基的IL。采用红外光谱对不同萃取体系中所萃出的沥青相进行分析发现,纯甲苯萃出的沥青相中检测到砂砾物质,而6种ILs辅助甲苯所萃取出的沥青中的砂砾含量则在红外检出限以下。丙酮/正庚烷复合溶剂及在6种ILs辅助下萃出的沥青相中均未检测到细小砂砾物质。实验结果为如何筛选适当ILs应用于非常规石油分离提供了科学基础。     

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。     

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。     

Determination of residual organic matter in extracted oil sands using a low temperature ashing method

The application of a low temperature ashing method for estimating total residual organic matter (toluene insolubles) in oil sands is described. A linear correlation exists between organic carbon content and loss on ignition at 400 ± 10 °C of solvent extracted oil sands. The ratio between total organic carbon and the weight loss on ignition (CT/LOl) owing to the removal of residual organic matter is much lower than that obtained for toluene soluble bitumen fractions, indicating very different chemical composition for the residual organic matter. The measured carbon content of the residual organic matter in oil sands suggests that this material could be a mixture of various fractions contained in resins, asphaltenes, asphaltic acids and humic acids.     

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。     

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.     

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     

Laboratory study of solvent enhanced communication in oil sands

Miscible displacement experiments were carried out to evaluate the potential of solvents in enlarging fractures between wells to allow for larger volumes of steam to be injected during in situ recovery operations in the Athabasca oil sands deposit. The solvents tested included carbon disulfide, toluene and a series of refinery streams and diesel oils. Since incomplete miscibility between bitumen and some solvents caused asphaltenes to precipitate, solvents were ranked in terms of bitumen compatibility. Solvents such as diesel DP-40 and diesel DC-40, which are intermediate in terms of solubilizing bitumen, were the most efficient in developing zones of low bitumen saturation around an initial fracture and at the same time not extracting bitumen from other regions of the bed. The effects of flow rate and cell orientation on solvent efficiency and permeability are also described. Solvent losses corresponded to about the residual saturation of oil after waterflooding.     

Study of pyrolysis kinetics of Alberta oil sand by thermogravimetric analysis

The kinetics of the thermal decomposition of Alberta oil sand has been investigated by thermogravimetric analysis (TGA) for the study of oil sand pyrolysis characteristics. The TGA experiments were carried out at four different heating rates of 10, 20, 30, 40 °C/min up to 900 °C to verify weight variation and reaction temperature. The activation energy of the thermal decomposition of Alberta oil sand obtained from the kinetic analysis was similar to that of the previous researches. Also, bitumen was extracted by solvent (toluene, THF (tetrahydrofuran)) and analyzed. Extracted bitumen was analyzed by using proximate analysis, ultimate analysis, heavy metal analysis, heating value, asphaltenes, API, SIMDIS, density, TLC, and molecular weight. The analyses of the extracted bitumen were similar to those of heavy residue.     

Analysis of Solvent‐Diluted Bitumen from Oil Sands Froth Treatment Using NIR Spectroscopy

Process control and optimization of bitumen froth treatment during oil sands processing require rapid analysis of asphaltene content in bitumen, solvent‐tobitumen ratio (S/B), and the density of solvent‐diluted bitumen. NIR spectroscopy was employed to meet this requirement. The NIR system comprised a spectrometer with no moving parts coupled with a double‐pass transflectance probe via a fiber‐optic cable. Quantitative calibration models were established using partial leastsquares regression in latent variables. The standard errors of calibration were 0.20 wt% for 0 to 20 wt% asphaltenes in bitumen, 1.1 wt% for 20 to 100 wt% asphaltenes in bitumen, 0.1 for S/B of solvent‐diluted bitumen, and 0.0017 g/mL for density of solvent‐diluted bitumen. It was shown that the process conditions could be monitored through the spectral scores from principal component analysis.