Determination of Algerian Hassi-Messaoud asphaltene aromaticity with different solid-state NMR sequences

Algerian oil well deposit derived asphaltene fraction was characterized by different MAS/NMR sequences to investigate asphaltene aromaticity and the best cross-polarization contact time. The aromaticity was estimated by single pulse sequence (SP), Hahn-echo (HE), cross-polarization (CP) and variable cross-polarization (VACP) sequences. The values found ranging from 0.58 to 0.48 are of the same order of magnitude as ones published in the literature. The discrepancies between the values are thought to be relevant to both the specificity of each sequence and the asphaltene structure. Spectra band de-convolution enables us the determination of the average number of carbon atoms per side chain according to each sequence. The obtained values spanning from 3 to 7 are also sequence nature dependent.     

Molecular size and weight of asphaltene and asphaltene solubility fractions from coals, crude oils and bitumen

The molecular weight of asphaltenes has been a controversy for several decades. In recent years, several techniques have converged on the size of the fused ring system; indicating that chromophores in virgin crude oil asphaltenes typically have 4-10 fused rings. Consequently, the molecular weight debate is equivalent to determining whether asphaltenes are monomeric (one fused-ring system per molecule) or whether they are polymeric. Time-resolved fluorescence depolarization (FD) is employed here to interrogate the absolute size of asphaltene molecules and to determine the relation of the size of the fused ring system to that of the corresponding molecule. Coal, petroleum and bitumen asphaltenes are compared. Molecular size of coal asphaltenes obtained here by FD-determined rotational diffusion match closely with Taylor-dispersion-derived translational diffusion measurements with UV absorption [1]. Coal asphaltenes are smaller than petroleum asphaltenes. N-methyl pyrrolidinone (NMP) soluble and insoluble fractions are examined. NMP soluble and insoluble fractions of asphaltenes are monomeric. It is suggested that the ‘giant’ asphaltene molecules reported from SEC studies using NMP as the eluting solvent may actually be the expected flocs of asphaltene which are not soluble in NMP. Data is presented that intramolecular electronic relaxation in asphaltenes does not perturb FD results.     

Investigation of asphaltene molecular weights

The molecular weights of asphaltenes, as determined by vapour-pressure osmometry, vary considerably and are dependent upon the nature of the solvent as well as the temperature. The data are interpreted in terms of association (of the asphaltene units) in solvents of low dielectric constant and dissociation in solvents of high dielectric constant. Data derived by means of a viscometric method yield inconsistent values for asphaltene molecular weights, and recognition of these inconsistencies causes some revision of the theory of the physical structure of petroleums, bitumens and asphalts.     

Phase behavior analysis of heavy oil containing asphaltene

A thermodynamic asphaltene precipitation model was developed based on the model of Nghiem et al. using the Peng-Robinson equation of state (PR EOS). This model calculates the amount of asphaltene precipitation based on changes in temperature and pressure. The effects of asphaltene precipitation on rock properties were investigated by observing changes in porosity and permeability. In this model, phase equilibrium was achieved by repeatedly reducing the amount of the asphaltene component, in contrast to the model of Qin et al. using the secant method. The results of this model were compared with experimental data of measured precipitation, based on changes in pressure, and agreed more closely than the model of Qin et al. Our results also confirmed that the maximum precipitation of asphaltene occurred at the bubble-point pressure. Thus, using the model, we verified that the precipitation pattern of asphaltene depended on temperature and pressure, and it is expected that changing patterns in reservoir productivity can be analyzed using asphaltene precipitation in heavy oil-containing asphaltene.     

驱油用水解聚丙烯酰胺分子量测定方法研究进展

聚合物分子量及分子量分布是水解聚丙烯酰胺评价和合成研究的重要指标之一,在研究其黏度、水力学半径、降解规律和聚合物筛选评价等方面有着重要应用。本文简要回顾了黏度法、光散射法、凝胶色谱法、联用技术、场流技术的基本原理及在测定水解聚丙烯酰胺分子量中的应用及发展情况。黏度法设备简单,对操作人员要求较低,易于掌握,是目前主要评价手段;光散射法对样品除尘等要求较高,主要用于机理研究与分析,在大庆油田已有应用;驱油用的水解聚丙烯酰胺由于分子量大、非体积效应显著,应用凝胶色谱技术测其分子量还需要做大量的研究工作;场流技术能有效解决聚合物分子的剪切断裂问题,具有比较广阔的发展前景。     

Average molecular weight of oil fractions by nuclear magnetic resonance

Average molecular weight (AMW) is an important parameter of the ‘average molecule’ in oil fractions. Normally it is measured by vapour pressure osmometry (VPO), but it would be useful to have an alternative measurement. A simple algorithm based on data from the n.m.r. spectra for the calculation of a maximum AMW, considering molecules with fully extended aromatic nuclei (cata-condensed molecules), and of a minimum AMW, considering molecules with maximum condensation of the aromatic nuclei, is presented in this paper. The values obtained are consistent with VPO values for different fractions as distillates, residues or asphaltenes. This method completes the data for a full characterization of the average molecule using only n.m.r..     

Effect of heavy asphaltene on stability of residual oil

An asphaltene fractionation method was developed in order to investigate the effect of heptane (n-C7) insoluble asphaltene (C7-asphaltene) on residual oil stability. C7-asphaltene was separated into heavy and light fractions by a new method using a binary solvent system of toluene and heptane (n-C7). It was found that the heavy fraction of C7-asphaltene in residual oil, extracted by this method, consisted of highly condensed polynuclear aromatics. Our new fractionation method and the Heithaus stability evaluation method were applied to hydroprocessed residual oils. The peptizability of heavy fraction of C7-asphaltene defined by the Heithaus method decreased in accordance with structural condensation of that fraction. On the other hand, light fraction of C7-asphaltene was considered to influence the peptizing power. We proposed a new conceptual model: light asphaltenes would perform as peptizing material as well as resin, and heavy asphaltene would be peptized in oil. This model introduced from our new asphaltene fractionation method could be more effective for understanding the destabilization phenomenon of residual oil.     

Shear,tack, and peel of polyisobutylene: Effect of molecular weight and molecular weight distribution

The effect of polymeric molecular weight and molecular weight distribution on pressure-sensitive adhesive performance was studied in a model system of commercial polyisobutylenes. Molecular weight was characterized by size exclusion chromatography and membrane osmometry. Pressure sensitive adhesive performance was assessed by shear, peel, and probe tack testing based on standardized test methods. Lower molecular weight polyisobutylenes (Mw < 600,000) are successful in peel and probe tack testing due to their ability to flow quickly and wet the substrate test surface. They do not function as well in shear, however, where the polymer must resist flow under a load. High molecular weight species, by contrast, perform well in shear resistance tests and less successfully in peel and probe tack testing. Where high and low molecular weight polyisobutylenes are blended to broaden the molecular weight distribution while maintaining constant weight average molecular weight, adhesive performance in shear, peel, and probe tack are improved. All of the adhesive properties tested were found to have their foundation in some fundamental rheological properties of the polymers (e.g., shear viscosity and tensile creep compliance). This suggests the use of fundamental rheological characterization for screening of adhesive formulations over more empirical adhesive testing methods.     

The molecular structure of asphaltene: an unfolding story

From detailed chemical and thermal degradation studies, a host of structural units have been identified in Alberta asphaltenes. It has been shown that the extent of aromatic condensation is low and that highly condensed pericyclic aromatic structures are present in very low concentrations. From the available data reported to date, it is concluded that petroleum asphaltenes were mainly derived through the catalytic cyclization, aromatization and condensation of n-alkanoic, probably fatty acids, precursors.     

微生物降解稠油中沥青质的研究进展

稠油因黏度高、流动性差,存在开采难度大、开发成本高的问题。沥青质等重组分含量高是造成稠油高黏度的主要原因。微生物通过降解重组分可降低稠油的平均分子量,从而降低稠油黏度。本文从沥青质的结构与组成出发,阐述了微生物对沥青质的降解机理,总结了近年来国内外最新研究进展,指出了目前微生物降解沥青质研究与应用所面临的挑战,并对其发展趋势做出了展望。微生物对沥青质的降解主要是通过将多环芳烃进行开环降解、将长链正构烷烃降解为短链、将杂环化合物进行开环除去杂原子三个方面。但因沥青质的分子量较大且组成有着不确定性,所筛选的微生物是否能够高效地降解储层中原油所含沥青质仍需进一步探究,因此高效沥青质降解菌株的筛选和利用基因工程等技术手段改造菌株应是未来工作的研究重点。此外,通过菌株的复配,利用菌株间的协同效应也可以达到更为高效降解沥青质的目的。     

Alternative procedure for the analysis of coal-derived materials for oil,asphaltene and pre-asphaltene content

An alternative method for the analysis of coal-derived materials for oil, asphaltene and pre-asphaltene content, is described. The test sample is coated as a thin layer on the fine mesh glass beads and the relevant fractions are extracted sequentially with hexane, toluene and pyridine. The efficiencies of the extractions are satisfactory. Solvents are removed subsequently from the extracts by evaporation at low pressure, and the residues are weighed. The method has been tested on a range of samples, and its sensitivity to sample loading and to co-solvent effects has been investigated.     

Studies of molecular weight distribution,particle morphology,and rheological behavior of ultra-high molecular weight suspension PVC

In this paper, the particle characteristics and rheological behavior of ultra-high molecular weight PVC (UHMWPVC) produced in both Japan and mainland China were studied. The molecular weight and its distribution of UHMWPVC were measured by GPC. By means of a series of techniques such as SEM, the measurement of surface pore size, plasticizer absorption, and photographic analysis, the morphology and general characteristics of UHMWPVC particles were investigated. A model of particle structure was proposed. It was found that compared to general PVC, UHMWPVC resins are more porous, having better plasticizer absorption properties. Similarly, compared to UHMWPVC made in mainland China, UHMWPVC made in Japan possesses particle characteristics preferred in PVC processing. In the studies of rheological behavior, the programmed temperature Brabender torque rheometer was used to study and compare the melting process of UHMWPVC resins and their plasticized systems under the same shear stress. The capillary rheometer and Brabender extrusion-rheometer were applied to investigate the rheological and extrusion properties of the plasticized systems mentioned above. The results showed that in melting and extrusion process, the particle characteristics of UHMWPVC result in the easy breakage of particles and the formation of “molecular flow,” On the other hand, the high molecular weight is unfavorable to processing. Generally speaking, much more research work is needed to improve the flow properties of UHMWPVC.     

沥青质和胶质对辽河稠油乳状液破乳的影响

针对辽河曙光稠油乳状液粘度大、破乳难、破乳温度高等问题,以曙光稠油为研究对象,从中分离出沥青质和胶质,用傅里叶变换红外光谱法分析其主要官能团,考察沥青质和胶质对稠油乳状液粘度及破乳效果的影响。测定了不同含量胶质、沥青质对稠油油／水界面张力的影响。结果证实,沥青质比胶质含有羟基多,分子间氢键作用强烈,更容易造成原油粘稠。随着叫（胶质）、训（沥青质）升高,稠油乳状液脱水率降低,w（沥青质）超过2．1％,或w（胶质）超过32％时,稠油乳状液的破乳十分困难。w（胶质）、w（沥青质）的增高会使破乳剂水溶液与原油的界面张力增大,w（沥青质）增加0．7％比叫（胶质）增加7％原油的界面张力升高还要大,所以训（沥青质）的增加对油水界面张力影响更大。     

BA原油沥青质性质及沉积抑制剂作用机理

原油开发中出现沥青质沉积问题,会导致油井及集输管线堵塞,从而影响原油正常生产和油田的高效开发。本文通过对BA原油中沥青质进行元素、XPS和FTIR分析,可知该沥青质表面官能团以碳氢化合物（C-C,C-H）为主,还含有硫酚和硫醇等脂肪类硫以及羧基等酸性官能团,可为沥青质沉积抑制剂的选择提供理论依据。抑制剂是通过破坏沥青质缔合体的相互作用来达到抑制聚沉的作用,利用激光粒度仪对原油加正庚烷（沉淀剂）后沥青质颗粒的粒度分布进行测定,结果表明：在油样中加入含有胺基碱性基团的抑制剂FAE183,能抑制沥青质的絮凝与沉淀,使沥青质颗粒的粒径显著减小。由抑制剂的作用机理分析可知,FAE183抑制剂与沥青质的主要作用机理为酸碱作用,并辅以氢键作用和偶极作用。     

蒸汽和金属盐作用下稠油粘度变化研究

探讨了在注蒸汽条件下,稠油的粘度随蒸汽温度、时间的变化规律。研究结果表明,在注蒸汽开采条件下,辽河稠油可以发生水热裂解反应。金属盐的存在,可以加速稠油的水热裂解反应,从而导致粘度降低,这为实现井下催化降粘开采稠油、就地提高稠油质量提供了理论依据。     

易沉积重油储层沥青质沉积特征及防治技术研究

M油田为碳酸盐岩储层,原油相对密度为0.9487,比重指数为17.65,属于重质原油.原油中沥青质质量分数为17.7％,高含量的沥青质在生产过程中易在井筒内沉积,导致井筒、电潜泵堵塞等问题,严重影响了该油田的正常生产.通过对原油特征、沥青质特征实验,得到了原油具体组成和胶体不稳定指数等原油特征,并得到了沥青质沉积物组成及具体结构特点、絮凝初始点、沉淀量等关键参数.在对原油和沥青质实验分析的基础之上,开展了沥青质沉积抑制剂、解除剂的筛选和优化实验,得到了适用于该油田的阳离子型沥青质沉积抑制剂和水基乳化低毒性沥青质解除剂体系.     

Rheological behaviors of fumed silica/low molecular weight hydroxyl silicone oil

The structure and viscoelastic properties of fumed silica gels in low molecular weight hydroxyl silicone oil were investigated by means of steady and dynamic rheology. It is found that the fumed silica/hydroxyl silicone oil suspension exhibits shear‐thickening under steady shear and “strain‐thickening” under oscillatory shear condition. Effects of hydroxy groups on the rheological behavior of silicone oil suspension with highly dispersed hydrophilic amorphous silica were investigated by infrared, ¹H‐NMR, and rheological test. The results show that the hydroxy groups on this system play an important role on the formation of shear thickening behavior of the suspension solution. At the same particle diameter and mass fraction, the amount of hydroxy groups on this system has a strong effect on increasing the viscosity of the suspension, which is likely due to multiassociation hydrogen bonding between liquid molecules and silanol groups on fumed silica surfaces (Si? OH). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40722.