沥青质分散剂对沥青质的稳定及缔合的影响

采用紫外－可见光谱法研究了沥青质分散剂对甲苯－正庚烷－沥青质体系中沥青质的稳定作用,通过黏度法考察了沥青质分散剂对沥青质溶液中胶束缔合度的影响。结果表明,十二醇（DAL）、十二烷基苯磺酸（DBSA）、十二烷基苯酚（DP）对沥青质都有一定的稳定作用。三种沥青质分散剂的稳定作用顺序为DBSA>DP>DAL。DAL、DP及DBSA浓度较低时（1%）对沥青质甲苯溶液黏度的影响规律相似,推迟了黏度迅速增加的拐点,即可以抑制沥青质胶束的缔合。DBSA浓度较大时,沥青质胶束没有明显的聚并,同时使得沥青质溶液的相对黏度增加明显。三种沥青质分散剂都能显著降低胶束的聚集数;三种沥青质分散剂抑制沥青质胶团聚并强弱顺序为：DBSA>DP>DAL。这与其头部官能团的酸性顺序一致。     

DPD Molecular Simulations of Asphaltene Adsorption on Hydrophilic Substrates: Effects of Polar Groups and Solubility

Adsorption of asphaltenes onto a polar substrate (e.g., a mineral) was modeled with dissipative particle dynamics (DPD) simulations, using continental asphaltene models. The adsorption mechanisms in 10–20% wt, of asphaltene in toluene/ heptane solutions were studied (well above the solubility limit). The structure in the adsorbed layer was highly sensitive to the presence of polar groups in the alkyl side chains and heteroatom content in the aromatic ring structure. Four types of asphaltene models were used: completely apolar (zero adsorption), apolar chains and polar heteroatoms, polar chains and no heteroatoms, and polar chains and heteroatoms (maximum adsorption). One hundred asphaltene monomers were distributed homogeneously in the solvent initially, in a ～(10 nm)³ domain.

Asphaltene monomers adsorbed irreversibly on the substrate via the polar group in the side chains, resulting in an average perpendicular orientation of the aromatic rings relative to the substrate. More frequent π–π stacking of the aromatic rings occurred for less solubility (more heptane), as in aggregates. With apolar side chains, only the heteroatoms in the aromatic ring structure had affinity to the substrate, but the ring plane did not have any preferred direction.

An important finding is that the aromatic ring assemblies “shielded” the substrate and polar groups that were anchored to the substrate, resulting in an effective non-polar surface layer seen by asphaltenes in the bulk, leading to much lower adsorption probability of the remaining asphaltenes. This “adsorption termination” effect leads to mono-layer formation. Continued adsorption with multilayering and reversible nanoaggregate adsorption occurred when both side chains in the model asphaltene (located on opposite sides of the aromatic sheet) contained polar groups, with a higher probability of exposing further polar groups to the bulk asphaltene. The general conclusion is that the number and position of the polar groups in side chains determine to a large degree the adsorption and aggregation behavior/efficiency of (continental) asphaltenes, in line with experimental evidence. The heteroatoms in the aromatic ring structure plays a more passive role in this context, only by providing organization via more π–π stacking in the adsorbed layer, and in aggregates.     

Effects of petroleum resins on asphaltene aggregation and water-in-oil emulsion formation

Asphaltenes from four crude oils were fractionated by precipitation in mixtures of heptane and toluene. Solubility profiles generated in the presence of resins (1:1 mass ratio) indicated the onset of asphaltene precipitation occurred at lower toluene volume fractions (0.1–0.2) than without resins. Small-angle neutron scattering (SANS) was performed on solutions of asphaltene fractions in mixtures of heptane and toluene with added resins to determine aggregate sizes. Water-in-oil emulsions of asphaltene–resin solutions were prepared and separated by a centrifuge method to determine the vol.% water resolved. In general, the addition of resins to asphaltenes reduced the aggregate size by disrupting the π–π and polar bonding interactions between asphaltene monomers. Interaction of resins with asphaltenic aggregates rendered the aggregates less interfacially active and thus reduced emulsion stability. The smallest aggregate sizes observed and the weakest emulsion stability at high resin to asphaltene (R/A) ratios presumably corresponded to asphaltenic monomers or small oligomers strongly interacting with resin molecules. It was often observed that, in the absence of resins, the more polar or higher molecular weight asphaltenes were insoluble in solutions of heptane and toluene. The addition of resins dissolved these insolubles and aggregate size by SANS increased until the solubility limit was reached. This corresponded approximately to the point of maximum emulsion stability. Asphaltene chemistry plays a vital role in dictating emulsion stability. The most polar species typically required significantly higher resin concentrations to disrupt asphaltene interactions and completely destabilize emulsions. Aggregation and film formation are likely driven by polar heteroatom interactions, such as hydrogen bonding, which allow asphaltenes to absorb, consolidate, and form cohesive films at the oil–water interface.     

Single molecule force spectroscopy of asphaltene aggregates

Asphaltene aggregation and deposition cause severe problems in nearly all phases of petroleum processing. To resolve those problems, understanding the aggregation mechanisms is a prerequisite and has attracted the interest of a great number of investigators. However, to date, the nature and extent of asphaltene aggregation remain widely debated. In the present study, we attempt to investigate asphaltene aggregation from a completely new perspective. The technique of single molecule force spectroscopy (SMFS) was used to investigate the response of single asphaltene aggregates under an external pulling force. Force curves representing the stretching of single asphaltene aggregates were obtained in simple electrolyte solutions (KCl and calcium) and organic solvents (toluene and heptane). These force curves were well-fitted by the modified worm-like chain model, indicating that those asphaltene aggregates acted like long-chain polymers under pulling by an external force. It was found that lower solution pH values and the presence of divalent cations resulted in a lower bending rigidity of the formed aggregates. The information retrieved from the force curves suggests that asphaltene molecules with a structure featuring small aromatic clusters connected by aliphatic chains do exist and that asphaltene aggregation could occur through a linear polymerization mechanism. The current study extends the application scope of SMFS.     

Studies of Athabasca asphaltene Langmuir films at air-water interface

Asphaltenes are present in heavy oils and bitumen. They are a mixture of hydrocarbons having complex structures of polyaromatic rings and short side chains. In general, the high-molecular-weight asphaltene is the most aromatic fraction with the highest number of side chains and the low-molecular-weight asphaltene contains the lowest number of side chains, while the number of side chains of the whole asphaltene fraction lies in between. In this study, asphaltenes were extracted and/or fractionated from Athabasca oil sand bitumen. Subfractions of high and low molecular weight and the whole asphaltenes were characterized using a Langmuir trough and complementary techniques such as VPO, FTIR, AFM, and contact angle measurements. At an air-water interface, amphiphilic asphaltene molecules can form a monolayer. Various fractions (high, low, and whole) of the asphaltene molecules behave similarly at the air-water interface, characterized by close resemblance of their surface pressure-area, hysteresis, and relaxation isotherms. The high-molecular-weight asphaltene is the most expanded fraction, while the low-molecular-weight asphaltene fraction is the most condensed, with the whole asphaltene lying in between. At the air-water interface a monolayer of the low-molecular-weight asphaltene relaxes at a faster rate than one of the high-molecular-weight asphaltene.     

Separation and characterization of petroleum asphaltene fractions by ESI FT-ICR MS and UV-vis spectrometer

Using heptane, toluene, and tetrahydrofuran (THF) as eluant, asphaltenes were fractionated into five fractions based on their polarity and solubility. The molecular composition of polar heteroatom species in both asphaltene and its fractions were analyzed by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The application of UV-vis spectrometer in characterizing asphaltene composition and measuring asphaltene concentration was discussed. About 11.9 wt% asphaltene components adsorbed permanently on silica gel in the extrography column after excessive elution with various solvents. In negative FT-ICR MS, the mass spectra show that acidic and neutral nitrogen-containing compounds such as N1 and N1S1 mainly existe in the first three less polar fractions, while oxygen-containing compounds such as O2 , O2S, O2S2 , O3 , and O4 show high relative abundance in more polar fractions. These results suggest oxygen-containing compounds have stronger adsorption ability with silica gel. It was observed that the double bond equivalence (DBE) distribution of N1 class species in the fractions shifted to higher values while the carbon number shifted to smaller numbers as polarity of fractions increased. This indicates that acidic and neutral N1 compounds with longer carbon chain and less aromaticity have less polarity compared with those with shorter carbon chain and stronger aromaticity. UV-vis absorbance indicats that fractions containing the most aromatic and most polar asphaltene have better absorbance at long wavelength, while the fractions that consist of least aromatic and least polar asphatlenes show high absorbance at short wavelength.     

Film forming properties of asphaltenes and resins. A comparative Langmuir– Blodgett study of crude oils from North Sea, European continent and Venezuela

 Asphaltenes and resins were separated from different crude oils, dissolved in different paraffinic and aromatic solvents and studied by means of Langmuir technique. It was found that the resin films are more compressible and more polar than the corresponding asphaltene films. Intermolecular aggregation between asphaltene molecules was more prominent than between resin molecules, and the size of the final aggregates depended on the nature of the solvent and the bulk concentration of the aggregating species. Even when present in smaller amounts than asphaltenes on the surface, the resins dominate the film properties. Received: 19 January 1998 Accepted: 15 April 1998     

小龙潭褐煤加氢液化及其重质产物结构表征

研究了小龙潭(XLT)褐煤直接加氢液化性能,并利用元素分析、红外光谱和荧光光谱法对液化重质产物沥青烯(AS)和前沥青烯(PA)结构进行了分析表征。结果表明,XLT褐煤液化活性高,FeS催化415 ℃时液化转化率最高达到89.6%,其液化过程主要是煤大分子结构热解并脱氧。所得AS和PA的芳环结构单元类似于原煤,氧主要以羟基和芳香酮羰基形式存在。PA具有"列岛"(archipelago)式大分子结构特征,芳香结构含量明显大于AS。THF溶液中,PA缔合作用显著强于AS,尤其在稀溶液中PA存在一定的分子内缔合。较高温度下所得PA和AS中芳香结构含量高,缔合作用强。     

Pyrolysis/gas chromatography/mass spectrometry of asphaltene fractions

Two n-heptane-precipitated asphaltene samples, characterized by elemental analysis and nuclear magnetic resonance spectrometry, were fractionated according to relative molecular size by gel permeation chromatography (GPC). Both the whole asphaltene samples and their fractions were analysed by pyrolysis/gas chromatography/mass spectrometry. The data obtained from the pyrograms (average side-chain length, aromaticity index, sulphur compounds vs. aliphatic compounds, presence of SO₂ and CO₂) demonstrated that, in the case of asphaltenes, GPC fractionation results in the separation of different chemical structures ranging from lower molecular mass, highly aromatic and polar compounds to higher molecular mass, less polar and aromatic compounds.     

渣油加氢处理前后沥青质的微观结构研究

采用元素分析、扫描电镜和透射电镜等分析方法对渣油原料中的沥青质、加氢处理后的沥青质及添加高芳香性轻循环油(LCO)反应后的沥青质进行对比研究。结果发现,渣油加氢处理前后沥青质的表面呈现出光滑表面和多孔的球形颗粒表面两种完全不同的形貌。渣油加氢前后沥青质的芳核堆砌表现出明显的长程无序局部有序的特征;加氢处理后的沥青质芳核片层易于堆砌,出现了多层堆砌、长程有序的类石墨结构。渣油中高芳香性LCO的添加有利于促进沥青质的加氢反应、改善沥青质芳核系统在渣油加氢处理过程中的聚集行为。     

渣油重组分沥青质结构分析及其对临氢热反应过程生焦的影响

以塔河常压渣油(THAR)为原料,正己烷为溶剂分离获得重组分C6-沥青质及其脱沥青油,并将所得沥青质回调至脱沥青油中配制成不同沥青质含量的渣油,以此为原料进行了高压釜临氢热反应实验。首先利用元素分析、1H-NM R及13CNM R、GPC分子量测定、FT-IR、XRD及SEM对沥青质的分子结构参数、官能团、晶体结构及表面形貌进行了分析研究。结果表明,该沥青质芳环侧链中长链部分较少且支链化程度较高,并以甲基、乙基、丙基结构为主,其芳香度fA高达0.57,芳环缩合程度及芳香片层结构较大,且芳香环系同时存在迫位缩合和渺位缩合的结构,已经形成连接致密的高芳香度结构。鉴于沥青质结构的复杂性,考察了其含量对临氢热反应过程的影响,结果表明,随着沥青质含量的增加,渣油的转化率逐渐增加,当沥青质含量超过5.12%时,其转化率的增加以快速生成焦炭为代价。另外,渣油中长链脂碳含量f3C与轻质油收率存在一定规律性,即随着f3C增加,轻质油收率先增加后趋于平缓,而残炭值、芳香度fA与焦炭收率表现出良好的线性关系。     

Langmuir films of asphaltene model compounds and their fluorescent properties

The relationship between the physicochemical properties of asphaltenes and asphaltene structure is an issue of increasing focus. Surface pressure-area isotherms of asphaltene model compounds have been investigated to gain more knowledge of their arrangement at an aqueous surface. Variations in interfacial activity have been correlated to proposed arrangements. The presence of a carboxylic acid has shown to be crucial for their interfacial activity and film properties. The acid group directs the molecules normal to the surface, forming a stable monolayer film. The high stability was absent when no acidic groups were present. Fluorescence spectra of deposited Langmuir-Blodgett films showed only the presence of the excimer emission for thin films of acidic model compounds, indicating a close face-to-face arrangement of the molecules. Time-correlated single photon counting (TCSPC) of the model compounds in toluene indicated the presence of aggregates for two of four compounds at low concentrations. However, a sudden drop of interfacial tension observed could not be correlated to the aggregation. Instead, aggregation induced by addition of a "poor" solvent showed decreased interfacial activity when aggregated due to decrease of monomers in bulk. The findings regarding these asphaltene model compounds and their structural differences show the great effect an acidic group has on their physicochemical properties.     

Pyrolysis of coal-tar asphaltene in supercritical water

Pyrolysis of coal-tar asphaltene, the main active component of coal tar in supercritical water (SCW), is investigated to further understand the upgrading mechanism of coal tar. It is found that coal-tar asphaltene convert to gas, maltene and char both in N₂ and in SCW, but the conversion of coal-tar asphaltene and the yield of maltene in SCW are significant higher than those in N₂. The effect of maltene and char in coal tar on the pyrolysis of coal-tar asphaltene is also studied. The results indicate that the presence of maltene could suppress the formation of char. And the addition of char could reduce the maltene yield. The analysis of pyrolysis product indicates the aromatic nucleus of asphaltene molecule is mainly composed of 2-4 rings aromatic hydrocarbons. Based on these results the pyrolysis mechanism of asphaltene in SCW was discussed.     

Fractal structure of asphaltene aggregates

A photographic technique coupled with image analysis was used to measure the size and fractal dimension of asphaltene aggregates formed in toluene-heptane solvent mixtures. First, asphaltene aggregates were examined in a Couette device and the fractal-like aggregate structures were quantified using boundary fractal dimension. The evolution of the floc structure with time was monitored. The relative rates of shear-induced aggregation and fragmentation/restructuring determine the steady-state floc structure. The average floc structure became more compact or more organized as the floc size distribution attained steady state. Moreover, the higher the shear rate is, the more compact the floc structure is at steady state. Second, the fractal dimensions of asphaltene aggregates were also determined in a free-settling test. The experimentally determined terminal settling velocities and characteristic lengths of the aggregates were utilized to estimate the 2D and 3D fractal dimensions. The size-density fractal dimension (D(3)) of the asphaltene aggregates was estimated to be in the range from 1.06 to 1.41. This relatively low fractal dimension suggests that the asphaltene aggregates are highly porous and very tenuous. The aggregates have a structure with extremely low space-filling capacity.     

Aromatically functionalized cyclic tricholate macrocycles: aggregation, transmembrane pore formation, flexibility, and cooperativity

The aggregation of macrocyclic oligocholates with introverted hydrophilic groups and aromatic side chains was studied by fluorescence spectroscopy and liposome leakage assays. Comparison between the solution and the membrane phase afforded insight into the solvophobically driven aggregation. The macrocycles stacked over one another in lipid membranes to form transmembrane nanopores, driven by a strong tendency of the water molecules in the interior of the amphiphilic macrocycles to aggregate in a nonpolar environment. The aromatic side chains provided spectroscopic signatures for stacking, as well as additional driving force for the aggregation. Smaller, more rigid macrocycles stacked better than larger, more flexible ones because the cholate building blocks in the latter could rotate outward and diminish the conformation needed for the water-templated hydrophobic stacking. The acceptor-acceptor interactions among naphthalenediimide (NDI) groups were more effective than the pyrene-NDI donor-acceptor interactions in promoting the transmembrane pore formation of the oligocholate macrocycles.     

Structure and dynamic properties of colloidal asphaltene aggregates

The abundant literature involving asphaltene often contrasts dynamic measurements of asphaltene solutions, highlighting the presence of small particle sizes between 1 and 3 nm, with static scattering measurements, revealing larger aggregates with a radius of gyration around 7 nm. This work demonstrates the complementary use of the two techniques: a homemade dynamic light scattering setup adapted to dark and fluorescent solutions, and small-angle X-ray and neutron scattering. Asphaltene solutions in toluene are prepared by a centrifugation separation to investigate asphaltene polydispersity. These experiments demonstrate that asphaltene solutions are made of Brownian colloidal aggregates. The hydrodynamic radii of asphaltene aggregates are between 5 and 10 nm, while their radii of gyration are roughly comparable, between 3.7 and 7.7 nm. A small fraction of asphaltenes with hydrodynamic and gyration radii around 40 nm is found in the pellet of the centrifugation tube. The fractal character of the largest clusters is observed from small angle scattering nearly on a decade length scale. Previous results on aggregation mechanisms are confirmed ( Eyssautier, J., et al. J. Phys. Chem. B 2011 , 115 , 6827 ): nanoaggregates of 3 nm radius, and with hydrodynamic properties also frequently illustrated in the literature, aggregate to form fractal clusters with a dispersity of aggregation number.     

沥青质含量对渣油加氢转化残渣油收率和性质的影响

以塔河常渣脱沥青油掺兑不同含量的沥青质为原料,于高压釜反应器内进行加氢转化反应实验,考察沥青质含量对渣油加氢转化残渣油收率和性质的影响。研究结果表明,随原料中沥青质含量的增加,加氢残渣油的收率逐渐降低,加氢残渣油中的沥青质和焦炭产量之和与原料中沥青质含量的比值逐渐减小,在实验选定的条件下,高沥青质含量时沥青质更倾向于发生氢解反应生成小分子组分。与原料相比,反应后所得>350 ℃残渣油的平均相对分子质量、H/C摩尔比减小,密度增大,硫含量降低,氮含量增加,饱和分和沥青质含量增加,芳香分及胶质含量降低。随渣油中沥青质含量的增加,硫、氮脱除率先增加后降低。     

煤液化沥青分析表征及结构模型

对从煤液化残渣中萃取出的沥青类物质进行了固体13C-CP/MAS NMR分析、元素分析、红外光谱分析(FT-IR)和光电子能谱(XPS)分析,得到煤液化沥青的芳香结构单元信息及相关结构参数信息。结果表明,煤液化沥青芳香桥碳与周碳之比为0.115,芳香碳原子的存在形式以苯结构为主;脂肪结构多以甲基和环状亚甲基形式存在;氧主要以羰基、酯基的形式存在;氮主要以吡咯的形式存在。利用结构参数和分析表征结果构建了煤液化沥青的大分子结构模型,并运用13C-NMR预测软件ACD/CNMR Predictor计算了煤精制沥青大分子结构模型的13C化学位移。根据计算结果对大分子结构模型进行了修正,获得了与实验谱图吻合较好的大分子结构模型。     

Two-step laser mass spectrometry of asphaltenes

Defined by their solubility in toluene and insolubility in n-heptane, asphaltenes are a highly aromatic, polydisperse mixture consisting of the heaviest and most polar fraction of crude oil. Although asphaltenes are critically important to the exploitation of conventional oil and are poised to rise in significance along with the exploitation of heavy oil, even as fundamental a quantity as their molecular weight distribution is unknown to within an order of magnitude. Laser desorption/ionization (LDI) mass spectra vary greatly with experimental parameters so are difficult to interpret: some groups favor high laser pulse energy measurements (yielding heavy molecular weights), arguing that high pulse energy is required to detect the heaviest components of this mixture; other groups favor low pulse energy measurements (yielding light molecular weights), arguing that low pulse energy is required to avoid aggregation in the plasma plume. Here we report asphaltene mass spectra recorded with two-step laser mass spectrometry (L2MS), in which desorption and ionization are decoupled and no plasma is produced. L2MS mass spectra of asphaltenes are insensitive to laser pulse energy and other parameters, demonstrating that the asphaltene molecular weight distribution can be measured without limitation from insufficient laser pulse energy or plasma-phase aggregation. These data resolve the controversy from LDI, showing that the asphaltene molecular weight distribution peaks near 600 Da and previous measurements reporting much heavier species suffered from aggregation effects.