基于正交试验的多聚磷酸复配SBS改性沥青粘弹性研究

为了探究多聚磷酸(PPA)复配SBS改性沥青组成材料对其粘弹性的影响,本文以SK90#基质沥青、SBS改性剂、抽出油、稳定剂、PPA、邻苯二甲酸二丁酯(DBP)为原材料,在正交试验设计的基础上,用高速剪切机制备了PPA复配SBS改性沥青,利用动态剪切流变仪分析了其粘弹特性.结果表明:(1)随着温度的升高,PPA复配SBS改性沥青的抗车辙因子随之降低、弹性减弱、抗永久变形能力降低,而其相位角增大、粘性增强、不可恢复变形能力提高.(2)当多聚磷酸的掺量为0.5％,复配改性沥青的其他组分选择最大掺量(均为3号水平)时提高了其粘弹性能,达到最优流变性能.(3)当PPA掺量为0.5％,SBS掺量为4％,抽出油掺量为2％,DBP为2％时,其复配改性沥青的性能最佳.     

Novel polymer aids for low‐grade oil sand ore processing

In the present study, a hybrid Al(OH)₃‐polyacrylamide (Al‐PAM) was synthesized and used in combination with a partially hydrolyzed polyacrylamide (HPAM) to process a low‐grade oil sand ore. It was found that Al‐PAM was capable to improve bitumen froth quality and tailings settling. But it led to deterioration in bitumen recovery due to the formation of large bitumen lumps during the bitumen extraction process. To resolve this problem, HPAM was added in combination with Al‐PAM as a dual system. The use of the dual system at a low dosage achieved a holistic improvement in bitumen recovery, froth quality, and tailings settling. To understand the role of Al‐PAM and the dual system in the bitumen extraction process, bitumen‐clay, bitumen‐bitumen, and clay‐sand interaction and adhesion forces were directly measured using an atomic force microscope (AFM). The measured forces indicate that bitumen recovery and tailings settling are controlled by the colloidal interaction and adhesion forces between the oil sand components.     

Effect of molecular weight and charge density on the performance of polyacrylamide in low‐grade oil sand ore processing

The effect of charge density and molecular weight (MW) of partially hydrolyzed polyacrylamide (HPAM) polymers on their performance in processing low‐grade oil sand ores was investigated. Bitumen extraction and tailings settling tests were carried out and an atomic force microscope (AFM) was used to directly measure the bitumen‐solid and solid‐solid interaction forces. It was found that HPAM polymers with a low MW acted as dispersants in the bitumen extraction process, resulting in low bitumen recovery and slow tailings settling but improved froth quality. In contrast, the use of HPAM polymers with a high MW improved both bitumen recovery and tailings settling but deteriorated froth quality. To achieve high bitumen recovery and fast tailings settling, a HPAM polymer must have a low to medium charge density (～30%) and a high MW (17.5 million Daltons). A stronger clay‐bitumen adhesion force normally resulted in a lower bitumen recovery. Fast tailings settling was achieved in the presence of a strong solid‐solid adhesion force.     

Understanding weathering of oil sands ores by atomic force microscopy

Effect of weathering on colloidal interactions between bitumen and oil sands solids was studied by atomic force microscopy (AFM). The change in bitumen chemistry due to weathering was found to have a negligible effect on the interactions of bitumen with solid particles. However, the increase in solid surface hydrophobicity due to ore weathering reversed the long‐range interaction forces between bitumen and solids from repulsive to attractive with a corresponding increase in adhesion force. The measured force profiles between bitumen and various solids can be well fitted with the extended DLVO theory by considering an additional attractive force. The attractive long‐range force and increased adhesion force make the separation of bitumen from solids more difficult and the attachment of fine solids on liberated bitumen easier, thereby leading to poor bitumen liberation and lower aeration efficiency. Such changes account for the observed poor processability of the weathered ores. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

An evaluation of supercritical fluid extraction as an analytical tool to determine fat in canola,flax, solin,and mustard

Supercritical fluid extraction (SFE) with carbon dioxide was used to extract oil from soft oilseeds (flax, solin, canola, and mustard). Oil content determinations from the SFE method AOCS Am 3–96, with and without ethanol as a modifier, were compared to results obtained with an exhaustive extraction using petroleum ether (FOSFA as in AOCS Am 2–93). Without the modifier, oil recoveries using SFE were 10 to 15% lower than oil contents by the FOSFA method for the flax and canola samples. For mustard, the oil recoveries by SFE were about 20 to 30% lower than oil contents by the FOSFA method. In the presence of the modifier, oil recoveries for flax and canola were about 3% lower than the FOSFA recoveries. Varying the time, temperature, and amount of modifier (ethanol) showed that recoveries increased with time, pressure, temperature, and amount of modifier independently of the oilseeds tested. Kinetics of the SFE extraction showed that the oil recoveries increased with the extraction time and reached a plateau after 60 min. Multiple extractions (2×30 min), however, gave better recoveries than a single extraction for the same amount of time (60 min). The best results were obtained using multiple extractions without modifier or a combination of multiple extractions first without and then with 15% modifier. Under these last two conditions, oil recoveries were close to 100% for flax, solin, and canola, but mustard oil recoveries were still 10% lower than recoveries using the FOSFA method. Mustard samples gave the lowest oil recovery from SFE when compared to FOSFA method recoveries whatever conditions were tested, suggesting a matrix effect on the oil recovery. The acyl lipid content of the various extracts was studied using the sum of all FA expressed as TAG as a measure of acyl lipid extraction. The acyl lipid contents of the extracts were close to 100% when no modifier was used during the SFE. In the presence of modifier, the acyl lipid contents of the extracts were 10 to 15% lower than the results obtained without modifier. The amount of acyl lipid in the extract decreased as the quantity of modifier increased. This suggests that increasing the ethanol modifier increased the amount of polar compounds extracted without significantly increasing the total amount of lipids. The FA profiles were constant throughout the various extraction procedures.     

SBS改性煤基沥青结构的研究

以SBS为改性剂,无水三氯化铝为引发剂改性煤基沥青为路用沥青。经测定,改性后沥青的软化点增加,针入度减小。SEM表明,改性沥青比原料沥青结构均匀。IR表明,沥青与SBS发生了化学反应。     

Rheological properties of styrene butadiene styrene polymer modified road bitumens

The use of polymers for the modification of bitumen in road paving applications has been growing rapidly over the last decade as government authorities and paving contractors seek to improve road life in the face of increased traffic. Currently, the most commonly used polymer for bitumen modification is the elastomer styrene butadiene styrene (SBS) followed by other polymers such as styrene butadiene rubber, ethylene vinyl acetate and polyethylene. This paper describes the polymer modification of two penetration grade bitumens with SBS. Six polymer modified bitumens (PMBs) were produced by mixing the bitumens from two crude oil sources with a linear SBS copolymer at three polymer contents. The rheological characteristics of the SBS PMBs were analysed by means of conventional as well as dynamic mechanical analysis using a dynamic shear rheometer (DSR). The results of the investigation indicate that the degree of SBS modification is a function of bitumen source, bitumen-polymer compatibility and polymer concentration, with the higher polymer concentrations in a high aromatic content bitumen producing a highly elastic network which increases the viscosity, complex modulus and elastic response of the PMB, particularly at high service temperatures. However, ageing of the SBS PMBs tends to result in a reduction of the molecular size of the SBS copolymer with a decrease in the elastic response of the modified road bitumen.     

Effect of material composition on antistripping performance of SBS modified asphalt mixture under dry and wet conditions

Styrene-butadiene-styrene (SBS) modified asphalt used in road engineering is a complicated mixture of various compositions. The present study was undertaken to evaluate the influence of different raw materials and their content on the moisture stability of SBS copolymer modified asphalt mixture. A total of 18 different combinations of base asphalt, SBS, furfural extract oil (FEO), and stabilizer were considered to prepare different SBS modified asphalt samples, and the contact angle test was carried out to determine the work of adhesion and the work of debonding of SBS modified asphalt with aggregate. Moreover, a multi-factor Analysis of Variance (ANOVA) was conducted to investigate the statistical effects of the material composition factors. The results show that the bond strength between SBS modified asphalt and aggregate is significantly affected by the source of base asphalt, but it is insensitive to the change of SBS type under dry and wet conditions. Besides, the moisture damage resistance of SBS modified asphalt improves firstly and then reduces with the rising storage of SBS, FEO, and stabilizer. Furthermore, linear regression analysis suggests that the work of adhesion under dry condition has excellent correlation with the work of debonding under wet condition.     

Capillary Curves for Ex‐situ Washing of Oil‐Coated Particles

The oil removal efficiency for the ex situ extraction of bitumen from oil sands, or ex situ washing of oil‐contaminated sand and related processes is determined by the balance of forces at the oil/water and solid/fluid interfaces. The objective of this work is to estimate the balance of forces at the interface using dimensionless numbers, and their use in evaluating and engineering ex situ soil washing processes. To this end, bitumen was removed from bitumen‐coated sand particles using a two‐step process. In the first step, the particles were mixed with a suitable solvent (toluene) used, primarily, to reduce the viscosity of bitumen. The particles were then mixed with water or an aqueous surfactant solution capable of producing low interfacial tensions with the solvent‐bitumen mixture. The fraction of oil retained after washing was evaluated as a function of interfacial tension, solvent/bitumen ratio, mixing time, mixing velocity, and particle size. These ex situ washing conditions were normalized using dimensionless film and particle‐based Weber and Capillary numbers. The fraction of oil retained by the particles was plotted against these dimensionless numbers to generate capillary curves similar to those used in enhanced oil recovery. These curves reveal the existence of a critical film‐based Weber number and a particle‐based Capillary number that can be used in the design or evaluation of soil washing processes. The film‐based Weber number also explained literature data that associates interfacial tension with the removal of oil from oil‐based drill cuttings, as well as field observations on the role that particle size plays on the removal of oil in soil washing operations.     

Silicon Nitride Colloidal Probe Measurements: Interparticle Forces and the Role of Surface-Segment Interactions in Poly(acrylic acid) Adsorption from Aqueous Solution

Direct measurements of forces between silicon nitride surfaces in the presence of poly(acrylic acid) (PAA) are presented. The force-distance curves were obtained at pH > pH_iep with an atomic force microscopy (AFM) colloidal-probe technique using a novel spherical silicon nitride probe attached to the AFM cantilever. We found that PAA adsorbs onto the negatively charged silicon nitride surface, which results in an increased repulsive surface potential. The steric contribution to the interparticle repulsion is small and the layer conformation remains flat even at high surface potentials or high ionic strength. The general features of the stabilization of ceramic powders with PAA are discussed; we suggest that PAA adsorbs onto silicon nitride by sequential adsorption of neighboring segments ("zipping"), which results in a flat conformation. In contrast, the long-range steric force found in the ZrO₂/PAA system at pH > pH_iep arises because the stretched equilibrium bulk conformation of the highly charged polymer is preserved via the formation of strong, irreversible surface-segment bonds on adsorption.     

Evaluation of rheological and image properties of styrene‐butadiene‐styrene and ethylene‐vinyl acetate polymer modified bitumens

This article presents a laboratory evaluation of conventional, fundamental, rheological, and morphological characteristics of styrene‐butadiene‐styrene (SBS) and ethylene vinyl acetate (EVA) polymer modified bitumens. Polymer modified bitumen (PMB) samples have been produced by mixing a 50/70 penetration grade unmodified (base) bitumen with SBS and EVA copolymer at different polymer contents. The fundamental viscoelastic properties of the PMBs were determined using dynamic (oscillatory) mechanical analysis and presented in the form of temperature and frequency‐dependent rheological parameters. The morphology of the samples as well as the percent area distribution of polymers throughout the base bitumen have been characterized and determined by means of fluorescent light optic microscopy and Qwin Plus image analysis software, respectively. The results indicated that polymer modification improved the conventional and rheological properties of the base bitumen. It was also concluded that the temperature and frequency had a significant effect on complex modulus of PMBs. The behavior of EVA and SBS PMBs had exhibited quite difference at 50°C. Moreover, it was found out that at low polymer contents, the samples revealed the existence of dispersed polymer particles in a continuous bitumen phase, whereas at high polymer contents a continuous polymer phase has been observed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Determining Surface Potential of the Bitumen‐Water Interface at Nanoscale Resolution using Atomic Force Microscopy

Atomic force microscopy (AFM) was used to measure the surface forces between a silicon nitride AFM tip and a deposited layer of Athabasca bitumen; the measurements were carried out in pure water (pH 6.0–6.5) and 1 mM KCl solution (pH 9). An AFM pyramidal‐shaped tip was moved stepwise using an operator‐controlled offset (10 nm per step) and the tip‐bitumen colloidal forces were measured at each location. Surface charge densities at the bitumen‐water interface were calculated from the measured colloidal forces using a theoretical model that combined both electrostatic and van der Waals forces for a conical tip‐flat substrate system. Fitted values of the bitumen surface charge density ranged from –0.002 to –0.004 C/m² in water (pH 6.0–6.5), and –0.005 to –0.022 C/m² in KCl solution (pH 9); the variation of local charge density along the bitumen surface appeared random. Bitumen surface potentials were also calculated from the surface charge densities using the Graham equation; the values ranged from –90 to –130 mV in water, and –45 to –110 mV in KCl solution. This study suggests the presence of bitumen surface domains of different surface charge densities/surface potentials. The domains are estimated to have characteristic sizes of 20 to 40 nm or less.     

Clay minerals in nonaqueous extraction of bitumen from Alberta oil sands: Part 1. Nonaqueous extraction procedure

A non-aqueous bitumen extraction process was studied where only toluene and heptane, with no water additions, were used to extract bitumen from two Alberta oil sands ore samples. One sample had a high bitumen (13.5 wt.%) and low fines (5.3 wt.% < 45 μm) contents, while the other sample had an intermediate bitumen (10.5 wt.%) and high fines (23.3 wt.%) contents. Bitumen recovery and product quality were measured under different process conditions such as the ratio of toluene to heptane and settling time. The Dean Stark procedure was used to determine the solids, bitumen and water contents of the extraction products. In addition, the water content was determined by the Karl Fischer titration method. High bitumen recovery was obtained for both oil sands ore samples although the high fines ore sample was more sensitive to the extraction conditions, especially the toluene to heptane ratio. A product with high purity, containing more than 99.5 wt.% bitumen on a solvent-free basis, was produced at room temperature under the optimum extraction conditions tested. The optimum settling time to achieve a pure product was less than 10 min, based on solids and water contents in the supernatant.     

Hydrophobic Interactions in Silane‐Treated Silica Suspensions and Bitumen Emulsions

In the extraction of bitumen from Canada's oil sands reserves, bitumen droplet coalescence is an important factor in determining the efficacy of the separation process. In a simplified analysis of bitumen droplet interactions, the relative contributions of classical DLVO and non‐DLVO forces occurring between a bitumen droplet and surface‐treated planar collector were evaluated using the impinging jet cell technique. Initial experiments were conducted using a system consisting of silane‐treated silica particles and a hydrophobic collector. This system is known to exhibit attractive non‐DLVO interactions as was clearly demonstrated by the present study. The attachment of bitumen droplets onto two different hydrophobic collectors was then examined. Results of these experiments indicate that bitumen droplet interactions involve an additional repulsive force that may be attributable to the heterogeneous nature of the droplet surface.     

Interaction between Bitumen and Fines in Oil Sands Extraction System: Implication to Bitumen Recovery

Colloidal interactions between bitumen and fines, extracted directly from oil sand ores, were investigated with zeta potential distribution measurement and surface force measurement using an atomic force microscope (AFM). Fines from good processing ores exhibit a negligible attachment to bitumen surfaces, due to hydrophilic nature of the fines. Fines from poor processing ores exhibit a stronger attachment to bitumen surfaces by an attractive hydrophobic force between bitumen and fines, due to hydrophobic nature of the fines and the presence of high concentration divalent cations in the processing water.     

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     

Characterization of Circle Cliffs oil sands of Utah

In the continuing characterization studies of Utah oil sands, this article was focused on the Circle Cliffs deposits which occur in the southeastern region of Utah. The bitumen was separated from the oil sand using a toluene extraction method. The extracted bitumen was fractionated using the modified SARA method and its fractional composition was compared to the other bitumens obtained from the Uinta Basin deposits. This comparison indicated that Circle Cliffs bitumen was unique among the Utah oil sand bitumens, particularly with respect to the chemical composition of its resin fraction, but showed resemblance with the Canadian Athabasca bitumen in some features. The effect of resin composition on the bitumen viscosity is discussed. Mineralogical analysis was performed on the solids, which indicated relatively large proportions of carbonate and kaolinite minerals. The undesirable effect of these minerals in the modified hot-water processing of Circle Cliffs oil sands is briefly discussed.     

Effect of montmorillonite on properties of styrene–butadiene–styrene copolymer modified bitumen

Clay/styrene–butadiene–styrene (SBS) modified bitumen composites were prepared by melt blending with different contents of sodium montmorillonite (Na‐MMT) and organophilic montmorillonite (OMMT). The structures of clay/SBS modified bitumen composites were characterized by XRD. The XRD results showed that Na‐MMT/SBS modified bitumen composites may form an intercalated structure, whereas the OMMT/SBS modified bitumen composites may form an exfoliated structure. Effects of MMT on physical properties, dynamic rheological behaviors, and aging properties of SBS modified bitumen were investigated. The addition of Na‐MMT and OMMT increases both the softening point and viscosity of SBS modified bitumens and the clay/SBS modified bitumens exhibited higher complex modulus, lower phase angle. The high‐temperature storage stability can also be improved by clay with a proper amount added. Furthermore, clay/SBS modified bitumen composites showed better resistance to aging than SBS modified bitumen, which was ascribed to barrier of the intercalated or exfoliated structure to oxygen, reducing efficiently the oxidation of bitumen, and the degradation of SBS. POLYM. ENG. SCI., 47:1289–1295, 2007. © 2007 Society of Plastics Engineers     

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。     

SBS对沥青性能的影响

通过测试软化点、针入度和延度对SBS改性沥青的性能进行表征.结果表明:使用线型或星型SBS作为沥青改性剂可以显著提高沥青性能.当硫黄稳定剂质量分数为0.2％,SBS质量分数为4％时,改性沥青的软化点、针入度和延度趋于稳定.此外,相较于线型SBS改性,星型SBS改性沥青的软化点稍高,针入度和延度相对更小.