Roles of Various Bitumen Components in the Stability of Water-in-Diluted-Bitumen Emulsions

An experimental study was conducted to evaluate the effectiveness of the various components of Athabasca bitumen in stabilizing water-in-diluted-bitumen emulsions. The solvent used to dilute the very viscous bitumen was a mixture of 50:50 by volume of hexane and toluene. The various bitumen components studied were asphaltenes, deasphalted bitumen, and fine solids. It was found that asphaltenes and fine solids were the main stabilizers of the water-in-diluted-bitumen emulsions. Individually, the two components can stabilize water-in-diluted-bitumen emulsions. However, when both are present the capacity of the diluted bitumen to stabilize water emulsions is greatest. Emulsion stabilization tests indicated that whole bitumen had less capacity to stabilize water emulsions than asphaltenes and solids. This would indicate that the presence of the small molecules within the whole bitumen tends to lower the emulsion stability. Deasphalted bitumen acts as a poor emulsion stabilizer. Although deasphalted bitumen led to the least emulsion stabilization capacity, interfacial tension measurements showed that diluted deasphalted bitumen gave a greater decrease in the interfacial tension of water with diluent.     

废轮胎热解油重质馏分制备的道路沥青老化性能研究

针对废轮胎热解油重质馏分(＞350℃)组成上具有蜡含量低,芳香分、胶质和沥青质含量高的特点,研究了废轮胎热解油重质馏分采用蒸馏法生产道路沥青的可行性。结果表明,废轮胎热解油中＞420℃、＞430℃、＞440℃三种渣油的性质可以满足不同牌号道路石油沥青老化实验前的技术指标,特别是延展性能优异,但是抗老化性能较差。渣油老化前后的族组成、官能团、氢分布及分子量分布变化表明,渣油在老化过程中存在氧化反应以及脱氢缩合反应,使渣油的化学组成发生变化,即芳香分、胶质含量减少,沥青质含量明显增加,使得沥青胶体体系中分散相明显增多而分散介质相对减少,造成热解油的渣油抗老化性能较差。     

储层沥青拉曼光谱特征及其对油气成藏期次的约束——以冀中坳陷杨税务潜山为例

快速准确确定油气成藏的时间及期次对于深入了解油气成藏机制与分布规律有着重要的意义。储层沥青作为油气成藏的标志物,通过对其分析有助于了解油气运移通道和准确判定油气成藏的时间。以杨税务潜山为例对储层沥青进行了系统的拉曼光谱分析。杨税务潜山储层沥青主要分布在最晚形成的裂缝中,少数充填在孔隙中。沥青在紫外光下基本不发荧光,属于炭质沥青。沥青的拉曼光谱特征相对比较稳定,具有明显的D峰和G峰,对于同一储层样品的不同测试点,D峰和G峰位置变化不大,但是背景噪声影响比较明显,拉曼谱图在1 500 cm-1之后具有明显的抬升。首先扣除原始拉曼光谱的背景值,然后采用洛伦兹分峰拟合方法对沥青拉曼光谱进行了分峰拟合,直到拟合的谱图曲线与原始谱图形态基本一致为止。在拟合好的谱图曲线上直接读取D峰和G峰的峰高（H）、半高宽（FWHM）,峰位差(v_G-v_D)、以及D峰和G峰之间的最低值（S）等参数,计算双峰之间的鞍型指数(saddle index),根据公式R_o%(cal)=-3.291+7.432log(v_G-v_D)-0.306log(saddle index)-2.935logFWHMG-3.118logFWHMD计算沥青的成熟度。结果显示储层沥青具有非均一性,指示油源具有混源特征,成熟度主要分布在两个区间,R_o分别为1.00～1.37和1.44～1.94。结合埋藏史确定杨税务潜山的油气成藏时间主要有两期,第一期为东营期（35～25 Ma）阶段,凝析油和湿气充注;第二期为明化镇-现今（5 Ma～0）阶段,以天然气为主充注。研究结果与研究区烃源岩生排烃史吻合,油气类型与杨税务潜山现今油气藏特征一致。研究表明,拉曼光谱技术可以对储层不同位置的沥青进行微区分析,并可以获得高精度的光谱数据,基于光谱数据可以准确确定沥青的成熟度。因此,基于储层沥青拉曼光谱定量表征和成熟度定量计算,结合盆地埋藏史和热史模拟,可以准确确定油气成藏的期次和时间。该方法具有快速准确、成本低的特点,展示了很好的应用前景。     

Evaluation of co-volume mixing rules for bitumen liquid density and bubble pressure estimation

The Peng–Robinson cubic equation of state (CEOS) is widely used to predict thermodynamic properties of pure fluids and mixtures. The usual implementation of this CEOS requires critical properties of each pure component and combining rules for mixtures. Determining critical properties for components of heavy asymmetric mixtures such as bitumen is a challenge due to thermolysis at elevated temperatures. Group contribution (GC) methods were applied for the determination of critical properties of molecular representations developed by Sheremata for Athabasca vacuum tower bottoms (VTB). In contrast to other GC methods evaluated, the Marrero–Gani GC method yielded estimated critical properties with realistic, non-negative values, followed more consistent trends with molar mass and yielded normal boiling points consistent with high temperature simulated distillation data. Application of classical mixing rules to a heavy asymmetric mixture such as bitumen yields saturated liquid density and bubble pressure estimates in qualitative agreement with experimental data. However the errors are too large for engineering calculations. In this work, new composite mixing rules for computing co-volumes of asymmetric mixtures are developed and evaluated. For example, composite mixing rules give improved bubble point predictions for the binary mixture ethane + n-tetratetracontane. For VTB and VTB + decane mixtures the new composite mixing rules showed encouraging results in predicting bubble point pressures and liquid phase densities.     

NMR Self-Diffusion and Transverse Relaxation Time in Bitumen: The Effect of Aging

In this investigation the dynamics of two types of bitumens with different penetration grade were tested by using dynamic shear rheometry (DSR) and Nuclear Magnetic Resonance (NMR) at unaged conditions, and upon both short- and long-term artificial aging. The gel-sol transition temperature was found to increase with increasing the time of aging treatment. Arrhenius parameters of the viscosity were found, unexpectedly, to be correlated with those of simple liquids, suggesting that the two kinds of systems, although chemically and physically quite different, share the same basic process at the molecular level. The molecular dynamics has been then investigated by NMR Pulsed Field Gradient Stimulated-Echo (PFGSE) and relaxometry (Carr-Purcell-Meiboom-Gill, CPMG, spin-echo pulse sequence) to capture the effect of aging upon dynamics variables such as self-diffusion coefficients D and transverse relaxation times T₂. The translational diffusion at T> of the light molecular components of both types of bitumens was characterized by broad distributions of D which were found independent of the experimental time scale up to 0.2 s. Similarly, T₂ data could be described as a continuous unimodal distributions of relaxation times determined both at T< and T> .