石油沥青质含硫结构的XANES导数光谱研究

采用X射线近边结构谱(XANES)研究沥青质中硫的存在形态,针对沥青质的未知复杂混合体系特性,采用高阶导数谱图分析方法,提高XANES的分辨率,准确分析沥青质中硫的存在形态;采用反正切和高斯函数分峰拟合、定量解析谱图,针对不同氧化态硫3p轨道空余状态不同引起1s→3p跃迁几率不同,提出峰面积修正因子,以准确分析体系中各形态硫的相对含量。结果表明,石油沥青质中硫主要存在形式为硫醚、噻吩、亚砜、噻吩砜和硫酸酯,常减压渣油沥青质中基本不含硫醚。     

煤沥青橡胶改质道路沥青老化研究：沥青质结构与官能团变化

利用1H-NMR核磁共振、VPO平均分子量以及IR光谱等分析方法,考察了煤沥青橡胶改质道路沥青中沥青质在老化过程中的结构与官能团变化。用B-L方法计算了沥青质平均结构参数。结果表明,沥青质是由6～7个缩合芳环构成,芳环四周仅含有极少的α、β侧链碳原子与少量N、O、S杂原子。比较老化过程中沥青质H分布与平均结构参数的变化,发现沥青质性质稳定。沥青质平均分子量的变化说明,在高温条件下老化时沥青质分子间发生缩聚反应。老化后羰基官能团的变化,表明沥青质分子间发生缔合作用。     

煤基和石油基C7-沥青质的结构特征及缔合行为

采用核磁(NMR)、小角散射分析(SAXS)、X射线光电子能谱(XPS)、改进的B-L法等手段,研究了煤基C7-沥青质(CT-asp)和石油基C7-沥青质(M-asp)两类沥青质的化学组成、官能团和分子结构等组成结构特征以及差异性,进而通过极性溶剂中沥青质稳定参数研究两类沥青质的缔合行为和聚集体尺寸以及两者之间的氢键和酸碱作用。结果表明,CT-asp分子芳香环数较少且有较多短烷基侧链,且芳香度较高,较高含量氧杂原子以芳香醚和酚羟基赋存形态为主;而M-asp的芳香核尺寸和平均相对分子质量明显高于CT-asp,芳香环数虽较多且有较多长烷基支链,且芳香度较小;两类沥青质缔合聚集程度关联物质的量比(n_(CT-asp)/n_(M-asp))及其分子结构特征,源于杂原子官能团的氢键和酸碱作用是两类沥青质缔合的主要作用力。     

大港常压渣油各组分平均偶极矩的研究

将大港常压渣油利用液相色谱法分成六个组分，测定了各组分的平均偶极矩。结果表明，渣油分子具有极性，饱和分和轻芳烃组分、重芳烃、轻胶质、中胶质、重胶质、沥青质的偶极矩依次增大，分别为1.19、2.88、3.79、4.92、6.36、11.70 Debye。元素分析表明，从饱和分和轻芳烃组分到沥青质组分，H/C原子比逐渐下降，表明H/C原子比减小与平均偶极矩增大有关；从饱和分和轻芳烃组分到沥青质组分，S/C、N/C原子比总体呈现上升趋势，渣油组分的杂原子含量与其极性有一定的关系，但两者并不完全一致，渣油组分分子的平均偶极矩还受到其他因素的影响。     

沥青质及其亚组分与烷基苯磺酸盐溶液在降低界面张力中的协同作用

利用混合溶剂沉淀法将原油中的沥青质分为4个亚组分, 研究了含有各组分的模拟油与烷基苯磺酸钠(p-S14-4, p为对二甲苯; 14表示烷基链上有14个碳原子; S表示表面活性剂; 4表示芳基在长链烷基的4号碳原子上)水溶液间的动态界面张力(DIFTs). 结果表明, 沥青质及其亚组分的分子尺寸、 浓度和极性对DIFTs有显著影响. 分子尺寸较大的沥青质亚组分与p-S14-4分子之间难以形成混合吸附膜, 协同作用较弱, DIFTs曲线呈“L”形, 最小界面张力(IFT_min)受浓度和极性的影响较小. 在高浓度时, 分子尺寸较小的沥青质及其亚组分快速扩散至界面与p-S14-4分子形成紧密的混合吸附膜, 能够快速降低界面张力(IFT); 随着时间的延长, 界面层的分子发生重排, 导致DIFTs曲线呈“V”形, 且在这种情况下沥青质及其亚组分的极性越高, 降低IFT的协同作用越明显, IFT_min越低.     

中东常压渣油热反应过程中沥青质的缔合性变化规律

用表面张力法研究了中东常压渣油热反应过程中正庚烷沥青质缔合性的变化。测定沥青质的不同浓度甲苯溶液的表面张力,利用溶液的临界胶束浓度表征沥青质的缔合性。定义蒸气压渗透法(VPO法)测得的沥青质平均分子量和表面张力法计算得到的平均分子量之比为沥青质的缔合度参数。结果表明,随着热反应的进行,在生焦诱导期内,沥青质的临界胶束浓度下降、沥青质缔合度参数增大,缔合性增强；达到生焦诱导期后临界胶束浓度上升、缔合度参数下降,缔合性下降。     

渣油超临界萃取馏分中硫化物的分离富集研究

采用选择性氧化与色谱结合的方法分离渣油中的硫醚硫化物和噻吩硫化物，该法是基于不同类型硫的选择性氧化、氧化组分与未氧化组分间极性的差异实现的。首先用高碘酸四丁铵在不氧化噻吩硫的情况下将硫醚硫选择性氧化为高极性的亚砜，经色谱柱分离富集后，利用红外色谱和硫元素分析仪，研究了馏分中硫化物的类型分布。结果表明,在俄罗斯渣油中噻吩硫和硫醚硫的质量分数随组分变重均呈增长趋势，噻吩硫相对质量分数(指硫醚硫+噻吩硫)随馏分变重呈下降趋势，相对质量分数在70%以上，噻吩硫是俄罗斯渣油中硫的主要存在形态。     

大港减压渣油的多层次分离与组成结构研究

采用超临界戊烷萃取分馏技术，分离了大港减压渣油，得到16个窄馏分和1个萃余残渣，对其组成和结构进行了表征；对超临界萃取分离窄馏分进行了四组分分离，研究了饱和分、芳香分、胶质和沥青质等亚组分的元素组成、相对分子质量分布和平均分子结构。结果表明，由窄馏分得到的四组分（SARA）性质结构差别很大，饱和分的平均分子结构最简单，芳香分的平均相对分子质量最小，胶质中的硫、氮含量最多，从萃余残渣中得到的沥青质相对分子质量分布范围最宽（200~40000）。     

钌离子催化氧化法研究大港减压渣油组分化学结构

利用钌离子催化氧化方法对大港减压渣油芳香分、胶质和庚烷沥青质进行了选择性降解，通过GC、GC-MS等分析手段对降解反应产物中一元正构脂肪酸、α,ω-二元正构脂肪酸和苯二～六元羧酸的含量和分布分别进行了定量分析。结果表明，芳香分、胶质和庚烷沥青质中的芳香结构上都存在大量烷基取代基和桥接不同芳碳的聚亚甲基桥。烷基取代基碳数最大约为33，聚亚甲基桥最大碳数约为24，而且这两种结构单元的含量均随碳数的增加而减少，并呈现出了偶碳优势。庚烷沥青质C12以下侧链相对较多而C16＋较少，与芳香分的分布相反；正构烷基侧链的浓度按庚烷沥青质、胶质和芳香分的顺序递减。降解产物中都检测到了苯二甲酸到苯六甲酸等一系列的苯多酸，表明三个组分中都存在稠环芳香结构。庚烷沥青质中缩合程度较高的迫位缩合结构含量最高，芳香分渺位缩合结构最多，胶质介于两者之间。     

煤焦油重组分沥青质性质分析及对加氢裂化生焦影响的推测

从中/低温煤焦油中切取重组分,提取了重组分C7-沥青质,并以此重组分为原料进行了高压釜加氢实验,通过1H-NMR、XRD、FT-IR、SEM、元素分析和相对分子量测定等手段对重组分沥青质结构参数、官能团、表观形态等方面进行了分析,并将其与加氢过程中生焦情况进行了关联。结果表明,C7-沥青质基本结构单元以稠环芳烃为中心,周围分布少而短的侧链,侧链以小于3个碳的短直链正构烷基为主,相对分子量小,芳香片层没有堆积结构。O是该沥青质中氢键主要来源,大多分布在环氧烷烃和醚类结构中,外围的O数量低,分子间氢键更难形成,结构单元之间缔合性弱,沉积聚合慢而均匀。沥青质中短侧链不易断裂,在反应过程中产生的稠环芳烃自由基少,缩合能力小,使该馏分油生焦能力低,具有较高的加氢潜质。     

Influence of aggregation of asphaltenes on the rheological properties of oil

Photon correlation spectroscopy was used to determine the threshold concentrations of n-heptane for phase transitions of asphaltenes in model systems for two types of oil. The rheological properties exhibited by high-paraffin oil in the asphaltene aggregation process were analyzed. It was shown that the presence of resin and paraffi n fractions in oil prevents phase transition of asphaltenes at the threshold concentration of n-heptane for the model system, so that a higher precipitant concentrations is required for aggregation of asphaltenes and formation of oil sludge.     

Experimental Study of Asphaltenes Flocculation Onset in Crude Oils Using the Densitometry Measurement Technique

The asphaltenes flocculation proceeds with changes of oil composition and causes significant losses in petroleum industry operations. The main objective of this work is to evaluate the reliability of the densitometry technique in studying experimentally the mechanism of aggregation and flocculation of asphaltenes occurring in crude oils. As asphaltene flocculation threshold in crude oils or mixture can be achieved by addition of n-heptane, various n-heptane concentrations were added to crude oil, and their effects have been investigated trough density measurements. Thereby, measurements were based on mixture of crude oil + toluene and cyclohexane + n-heptane, respectively. While asphaltene aggregates form clusters and flocculate, the mixture volumetric mass change and the reduced density of non-Newtonian fluids under investigation have been pointed out as one of appropriate measures of flocculation process. In particular, the curve representing the reduced density as function of the ratio between n-heptane concentration and concentration of crude oil under study featured a break point that well characterizes the flocculation threshold. Besides the quantity needed to initiate and to aggregate asphaltenes within crude oils, the amount required to completely achieve deposition of asphaltenes has also been identified. A quantity of 4 and 20 g of n-heptane per gram of crude oil was found necessary.     

Determining the interaction and characterization of asphaltene in alkylbenzene solvents using nuclear-electron double resonance

This study uses ¹H dynamic nuclear polarization (DNP) methods to determine asphaltene aggregates and the interaction between asphaltene extracted from MC800 asphalt and alkylbenzene solvents, as well as elemental analysis for the characterization of asphaltene. The asphaltene sample was characterized using the elemental analysis of carbon (C), hydrogen (H), nitrogen (N), and sulfur (S). The results show that asphaltenes have the highest carbon content. The sulfur and hydrogen contents are nearly the same and nitrogen content is the smallest. The DNP data provided good results for characterizing asphaltene behavior in alkylbenzene solvents.     

Water-in-Oil Emulsions Stabilized by Asphaltenes Obtained from Venezuelan Crude Oils

W/O emulsions were studied using asphaltenes as surfactants. Asphaltenes were obtained from three Venezuelan crude oils: “Lago Cinco,” “Rosa Mediano,” and “Ayacucho.” They were extracted using n-heptane as a precipitanting agent. The following variables were studied: concentration of asphaltenes in the oleic phase and pH of the aqueous phase. An increase in asphaltene concentration in the oleic phase increases emulsion stability. On the other hand, the most stable emulsions correspond to an alkaline aqueous phase. Likewise, emulsion stability was higher for asphaltenes obtained from “Lago Cinco” crude oil and lowest from Rosa Mediano asphaltenes.     

石油沥青质的NMR测定及其模型分子推测

从6种不同原油中分离提取了正己烷不溶的沥青质，测定了沥青质的1H NMR(Nuclear Magnetic Resonance)和13C NMR谱，从不同类型氢和碳原子的质量分数计算得到了一系列平均结构参数，结合相对分子质量测定和元素分析，给出了沥青质基本结构单元的平均分子式，推测了模型分子的结构。结果表明，沥青质的基本结构单元可以用稠环芳烃连接环烷烃和烷基侧链并含氧、氮和硫等杂原子的单元表示，结构单元之间形成缔合体，缔合数为4～6。     

Interfacial rheology of petroleum asphaltenes at the oil-water interface

A biconical bob interfacial shear rheometer was used to study the mechanical properties of asphaltenic films adsorbed at the oil-water interface. Solutions of asphaltenes isolated from four crude oils were dissolved in a model oil of heptane and toluene and allowed to adsorb and age in contact with water. Film elasticity (G') values were measured over a period of several days, and yield stresses and film masses were determined at the end of testing. The degree of film consolidation was determined from ratios of G'/film mass and yield stress/G'. Asphaltenes with higher concentrations of heavy metals (Ni, 330-360 ppm; V, 950-1000 ppm), lower aromaticity (H/C, 1.24-1.29), and higher polarity (N, 1.87-1.99) formed films of high elasticity, yield stress, and consolidation. Rapid adsorption kinetics and G' increases were seen when asphaltenes were near their solubility limit in heptane-toluene mixtures (approximately 50% (v/v) toluene). In solvents of greater aromaticity, adsorption kinetics and film masses were reduced at comparable aging times. Poor film forming asphaltenes had yield stress/G' values ((1.01-1.21) x 10(-2)) more than 4-fold lower than those of good film forming asphaltenes. n-heptane asphaltenes fractionated by filtering solutions prepared at low aromaticity (approximately 40% toluene in mixtures of heptane and toluene) possessed higher concentrations of heavy metals and nitrogen and higher aromaticity. The less soluble fractions of good film forming asphaltenes exhibited enhanced adsorption kinetics and higher G' and yield stress values in pure toluene. Replacing the asphaltene solutions with neat heptane-toluene highlighted the ability of films to consolidate and become more elastic over several hours. Adding resins in solution to a partially consolidated film caused a rapid reduction in elasticity followed by gradual but modest consolidation. This study is among the first to directly relate asphaltene chemistry to adsorption kinetics, adsorbed film mechanical properties, and consolidation kinetics.     

Asphaltene self-association and water-in-hydrocarbon emulsions

The configuration of asphaltenes on the water-oil interface was evaluated from a combination of molar mass, interfacial tension, drop size distribution, and gravimetric measurements of model emulsions consisting of asphaltenes, toluene, heptane, and water. Molar mass measurements were required because asphaltenes self-associate and the level of self-association varies with asphaltene concentration, the resin content, solvent type, and temperature. Plots of interfacial tension versus the log of asphaltene molar concentration were employed to determine the average interfacial area of asphaltene molecules on the interface. The moles of asphaltenes per area of emulsion interface were determined from the molar mass data as well as drop size distributions and gravimetric measurements of the model emulsions. The results indicate that asphaltenes form monolayers on the interface even at concentrations as high as 40 kg/m(3). As well, large aggregates with molar masses exceeding approximately 10,000 g/mol did not appear to adsorb at the interface. The area occupied by the asphaltenes on the interface was constant indicating that self-associated asphaltenes simply extend further into the continuous phase than nonassociated asphaltenes. The thickness of the monolayer ranged from 2 to 9 nm.