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。     

油砂沥青分离技术研究进展

油砂作为一种储量丰富的非常规石油资源,越来越受到世界各国的广泛关注。对于油砂的加工利用,其前提就是油砂沥青的分离,因此对其技术的研究十分必要。本文首先介绍了油砂的组成及分类,然后着重对几种主要油砂分离技术（热水洗法、有机溶剂萃取法、超临界流体萃取法、超声波辅助萃取法、离子液体萃取法和热解干馏法）的优缺点进行了汇总,并详细分析了它们各自的分离流程。其中,热水洗法、有机溶剂萃取法和热解干馏法是目前研究相对成熟的3种方法,而其他方法虽然分离效果相对高,但是对工艺条件和设备的要求较高,导致较高的投资和运行成本,因此还需要对这些油砂沥青分离工艺进行更加深入的研究,以满足工业化应用的要求。最后,对油砂沥青分离技术的发展前景进行了展望。     

离子液体；石油沥青质的新型溶剂

The dissolution of petroleum asphaltenes with ionic liquids is studied for the first time. The results show that the ionic liquids could be used as novel solvents for asphaltenes. The important parameters governing the ability of ionic liquids for dissolution of asphaltenes are discussed. It is found that, the ionic liquids based on the cations containing a conjugated aromatic core or the anions which are strong hydrogen bond acceptors are most effective, whereas the ionic liquids containing ＇non coordinating＇ anions such as [BF4]^- and [PF6]^- are nonsolvents for asphaltenes. Increase in the effective anion charge density enhances the ability of ionic liquids to break the extensive asphaltene associations and thus enhances the solubility of asphaltenes in the ionic liquid. The dissolution ability of ionic liquid decreases apparently with increasing the substituted alkyl chain length of its cationic head ring. Temperature is found to play an important role on dissolution of asphaltenes, and the dissolution can be significantly imoroved bv microwave heatinz.     

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。     

离子液体对沥青质分散作用的研究

因为沥青质沉积在石油生产中可导致管线和水库全部或部分阻塞、改变润湿性和引起设备损坏(黏住导管和水库的壁)。离子液体用于处理原油以减少沥青质在原油中所占的量。研究沥青质的特性和离子液体对沥青质分散的影响。     

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。     

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。     

离子液体介质中沥青砂内重组分降解过程

This paper illustrates the reaction pattern of catalytic degradation of macromolecules in asphaltic sands. Such parameters as ionic liquid catalyst system and H^ proton donor, that affect the change of the organic phase and the mass of organic matter in residual phase of asphaltic sands, were investigated. It was found that chloroaluminate (Ⅲ) ionic liquid/H3PO4 systems as reaction medium was an effective catalyst system for asphaltic sands degradation. The catalytic degradation of asphaltic sand swas related to the kinds of chloroaluminate (Ⅲ) ionic liquids and H^ proton donor. In [BMIM] [AlCl4]/H3PO4 reaction catalytic medium, the degradation of asphaltenes in the organic phase reached 16.44 %, the degradation of asphaltenes in the residual phase reached 30.74%. TLC-FID analysis of asphaltic sands showed that the main degradation products were saturates and aromatics, and resin fractions as well. At a temperature close to oil-bearing formation and with absense of oxygen, the yield of H2S reached 74%,which indicated that catalytic degradation of sulphur-containing compounds was easier.     

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。     

油砂沥青超声波减粘工艺研究

油砂沥青粘度较大,自然状态下不易流动,严重影响了管道输送及加工,针对目前油砂沥青研究中存在的问题,采用超声波进行了减粘的实验研究。实验综合考察了超声波作用时间、温度、超声波频率、超声波功率等因素对减粘效果的影响。实验结果表明,在适当的超声作用时间(20 min)、适宜的温度(30℃)、适宜的超声波频率(20 kHz)和超声波功率(250 W)的条件下,油砂沥青的减粘率可达80%以上。经超声波处理后的油砂沥青粘度略有恢复,但仍远低于处理前的粘度,超声波减粘效果良好。     

油砂沥青溶剂提取回收组合工艺

采用有机溶剂提取-超临界CO2回收溶剂这一组合方法对加拿大Athabasca油砂进行了提取分离及溶剂回收实验,通过实验筛选出最佳抽提溶剂为重整汽油。溶剂提取的最佳工艺条件:提取温度80℃,溶剂流量60mL/min,提取时间60min。在此条件下油砂沥青提取率达到92.74%。对超临界CO2-重整汽油体系的相行为进行研究,并通过实验综合考察了温度、压力、CO2流量以及回收时间等工艺操作条件对溶剂回收的影响。结果表明:在回收温度50℃,回收压力13MPa,溶剂与CO2分离温度70℃,压力5MPa,CO2流量7.5L/h,时间1h的条件下,重整汽油的回收率为98.71%。     

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.     

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.     

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。     

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     

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.