Assessing the Maturity of Crude Petroleum Oils Using Total Synchronous Fluorescence Scan Spectra

There have been many applications of fluorescence methods for the analysis of crude petroleum oils down through the years. However, none of these studies has yielded a robust qualitative or quantitative method for quantifying the chemical composition, or assessing the maturity of crude oils. Simple fluorescence parameters such as lifetime, intensity, and intensity ratios do not correlate well with chemical composition particularly for medium weight crude oils [A. G. Ryder, T. J. Glynn, and M. Feely (2003). Proc. SPIE-Int. Soc. Opt. Eng. 4876, 1188-1195.]. A better approach may be to use the Total Synchronous Fluorescence Scan (TSFS) method to fully interrogate the complex chemical composition of the oils [D. Patra and A. K. Mishra (2002). Anal. Bioanal. Chem. 373, 304-309.]. We present TSFS spectra from 18 crude petroleum oils of varying composition, sourced from around the world. The TSFS plots of these oils are very complex, with the contours being spread over the full 250-700 nm wavelength range (lambda(ex)) and 40-200 nm wavelength interval (delta lambda) sampled. The 3-D contour maps tend to two contour concentrations one at lambda(em) < 300 nm, delta lambda = 120-200 nm, and a second near lambda(ex) approximately 380-400 nm, delta lambda = 40-60 nm. The first feature represents fluorescence emission originating mainly from energy transfer processes with the second, longer wavelength feature originating from fluorescence emission generated by a higher proportion of direct excitation as opposed to emission resulting from energy transfer. The topography of the 3D contour plots is therefore influenced by the balance between energy transfer and direct fluorescence emission, which is governed by the chemical composition of the crude oils. We discuss how the gross chemical composition affects TSFS spectra and how TSFS can be used to assess oil maturity with a view to developing quantitative methods.     

On thermal diffusion in binary and ternary Lennard-Jones mixtures by non-equilibrium molecular dynamics

Molecular simulation appears to be an alternative to experiment for the estimation of transport and thermodynamics properties of fluid mixtures, which is of primary importance in the evaluation of the initial state of a petroleum reservoir. In this study, a non-equilibrium molecular dynamics algorithm has been applied to mixtures of Lennard-Jones spheres in order to compute the thermal diffusion process. The pertinence of such an approach to simple alkane mixtures is shown. The separate influences on the thermal diffusion of the molecular features in binary equimolar mixtures are then summarized. Simulations on binary non-equimolar mixtures have been performed as well. The results indicate an increase in the thermal diffusion process with increasing molar fraction of the lightest component. Moreover, this increase is enhanced with increasing difference in the number of carbons between the two alkanes. Then, a simple method, which yields results consistent with simulations, is proposed to predict thermal diffusion for the whole range of molar fractions starting only from the equimolar value. Finally, for ternary mixtures, the law of the corresponding states is shown to be valid when the appropriate mixing rules are applied, which allows the estimation of thermal diffusion in such mixtures from equivalent binary mixtures.     

Magneto-optical activity of crude oil and its heavy fractions

We have experimentally studied optical and magneto-optical spectra of solutions of crude oils of different origin and their heavy fractions in the visible spectral range. Magnetic circular dichroism of oil in the wavelength range ??550 nm has been revealed. We show that the shape of the spectra of this dichroism depends on the origin of crude oil, with the magnetic dichroism magnitude being proportional to the concentration of the oil in the solution. A comparison of the data of magneto-optical spectroscopy with electron paramagnetic resonance spectra and chemical composition of samples has allowed us to conclude that the observed magneto-optical activity is determined by the occurrence of VO²⁺ complexes in the oil samples. The revealed magneto-optical activity of crude oil can form the basis of a unique method of analysis of the composition and properties of oils of different origin and heavy fractions thereof.     

Linewidth Analysis of Spin Labels in Liquids: II. Experimental

This work demonstrates that homogeneous linewidths can be extracted from continuous wave electron paramagnetic resonance spectra and that they quantitatively agree with the predictions of existing relaxation theory. We suggest that relaxation theory can be used to predict experimental lineshapes provided that the simulations properly include sources of broadening. We have found that the rotational correlation times for spin labels in different percentages of glycerol/water mixtures are best modeled by a power law treatment for the viscosity, similar to that for translational diffusion. The translational diffusion coefficients themselves also have a power law dependence on the viscosity for glycerol/water mixtures. The linewidths were linearly dependent upon both the oxygen and the spin label concentration. The hyperfine splittings of all nuclei were observed to decrease linearly with increasing spin label concentration, completely at odds with existing theory which predicts a quadratic dependence upon concentration. The linear dependence was independent of hyperfine splitting until the magnitude of the hyperfine splitting was less than the homogeneous linewidth.     

基于激光拉曼检测技术的输油管道原油鉴别方法

为降低长距离原油输送过程中混油产生的损失, 需定时检测管线原油成分以确定是否出现混油事故。常规检测输油管线原油成分需从现场管线中取样后, 再进行室内检测, 该类技术操作复杂且易受环境因素的影响, 未能实时反映管道混油后油品成分变化。文中应用激光拉曼光谱对原油识别检测进行了实验研究, 试验选取辽河油田不同区块2种原油, 通过特征峰及图谱分析, 实现不同类型原油的识别。结果表明, 2 800 cm-1~3 000 cm-1区域特征峰是激光拉曼证明烷烃存在的重要标志, 该段拉曼谱图特征峰的不同代表了烷烃组分的差异性, 可以有效区分不同类型的原油。该方法的进一步研究, 有望形成一套油品快速、实时检测的技术方法。     

Application of Fluorescence to the Study of Crude Petroleum

Crude petroleum oils are complex mixtures of different compounds (mainly organic), which are obtained from an extensive range of different geological sources. The fluorescence of crude petroleum oils derives largely from the aromatic hydrocarbon fraction, and this fluorescence emission is strongly influenced by the chemical composition (e.g., fluorophore and quencher concentrations) and physical characteristics (e.g., viscosity and optical density) of the oil. The fluorescence spectroscopy (FS) is increasingly used in petroleum technology due the availability of better optical detection techniques, because FS offers high sensitivity, good diagnostic potential, and relatively simple instrumentation. In this work we analyzed crude petroleum at different dilution in Nujol, a transparent mineral oil. The main objective of this work was to verify the possibility to measure crude oil emission spectroscopic without use of volatile solvents. The mixtures of nujol with different -crude oil concentrations were measured with a 10 mm optical path cuvette thus simplifying the fluorescence spectroscopy signal detection. The emission spectra were obtained by exciting the samples with a 400 W Xenon lamp at 350 nm, 450 nm and 532 nm. The emissions of the samples were collected perpendicularly with the excitation axis.     

Law of corresponding states and thermal-diffusion factor of Ne---Kr and Ar---Kr mixtures

New data of the thermal diffusion factor, α_T, for five Ne---Kr and four Ar---Kr mixtures in the low temperature range are given. It is shown that the dependence of α_T on the composition of these mixtures together with the thermodynamic and first-order transport properties of the noble gases can be interpreted consistently using the law of corresponding states proposed by Kestin, Ro and Wakeham. Moreover it is suggested that the thermal diffusion factor of these mixtures could also be interpreted by this law.     

NMR properties of petroleum reservoir fluids

NMR well logging of petroleum reservoir require the measurement of the NMR response of water, oil, and gas in the pore space of rocks at elevated temperatures and pressures. The viscosity of the oil may range from less than 1 cp to greater than 10,000 cp. Also, the oil and gas are not a single component but rather a broad distribution of components. The log mean T1 and T2 relaxation time of dead (gas free) crude oils are correlated with viscosity/temperature and Larmor frequency. The relaxation time of live oils deviate from the correlation for dead crude oils. This deviation can be correlated with the methane content of the oil. Natural gas in the reservoir has components other than methane. Mixing rules are developed to accommodate components such as ethane, propane, carbon dioxide, and nitrogen. Interpretation of NMR logs uses both relaxation and diffusion to distinguish the different fluids present in the formation. Crude oils have a broad spectrum of components but the relaxation time distribution and diffusion coefficient distribution are correlated. This correlation is used to distinguish crude oil from the response of water in the pores of the rock. This correlation can also be used to estimate viscosity of the crude oil.     

Effect of oxygen on the NMR relaxation properties of crude oils

Nuclear magnetic resonance relaxation measurements of bulk fluids provide a sensitive probe of the dynamics of molecular motion. Dissolved oxygen can interfere with this technique as its paramagnetic nature leads to a reduction of the paramagnetic relaxation times of the fluids. We studied this effect for the relaxation properties of crude oils that are in general characterized by a distribution of relaxation times. The samples were stock tank oils that have been exposed to air. We comparedT ₁ andT ₂ relaxation time distributions and their correlation functions of the initial (oxygenated) samples with those from the deoxygenated samples. Oxygen was removed from the oils with a freeze-thaw technique. As expected, the effect of oxygen is most apparent in oils with long relaxation times. In these oils the effect of oxygen can be described by an additional relaxation rate 1/T _1,2 ^ox to the transverse and longitudinal relaxation rates that is sample dependent but does not vary within the relaxation time distribution of the oil. Values of 1/T _1,2 ^ox for different crude oils were found to be in the range of 2.5 to 8.3 s. For crude oils that have components with relaxation times less than 100 ms, no significant oxygen effect is observed.     

Dynamical screening and ionic conductivity in water from ab initio simulations

We present a method to calculate ionic conductivities of complex fluids from ab initio simulations. This is achieved by combining density functional theory molecular dynamics simulations with polarization theory. Conductivities are then obtained via a Green-Kubo formula using time-dependent effective charges of electronically screened ions. The method is applied to two different phases of warm dense water. We observe large fluctuations in the effective charges; protons can transport effective charges greater than +e for ultrashort time scales. Furthermore, we compare our results with a simpler model of ionic conductivity in water that is based on diffusion coefficients. Our approach can be directly applied to study ionic conductivities of electronically insulating materials of arbitrary composition, e.g., complex molecular mixtures under such extreme conditions that occur deep inside giant planets.     

Isotopic thermal diffusion factors of the noble gases

A new set of isotopic thermal diffusion factors for Ar, Kr and Xe is reported. The data have been obtained from thermal diffusion column measurements in a column previously calibrated with Ne gas, and complete the α_T data for the binary mixtures of noble gases given previously. The results lead to the conclusion that the thermal diffusion properties of the noble gases and their mixtures are well described by the law of corresponding states first proposed by Kestin, Ro and Wakeham. It is also concluded that the calibration technique used makes the thermal diffusion column a valuable instrument for the determination of the thermal diffusion factors of isotopic and non-isotopic dilute gas mixtures.     

Diffusion-relaxation distribution functions of miscible fluids measured in grossly inhomogeneous fields

In this paper, the recently developed technique of measuring diffusion-relaxation distribution functions in grossly inhomogeneous fields was applied to the characterization of bulk fluids. The measurements were conducted in a static stray field of a superconducting magnet at a Larmor frequency of 5 MHz, relevant for ex situ nuclear magnetic resonance applications in oil-well logging or materials testing. Results are presented for samples of water and hydrocarbon oils, including a number of crude oils. The measurements indicate strong correlations between diffusion coefficients and relaxation times that are sample specific. The diffusion-relaxation correlation function provides information on the correlation between the rotational and the translational diffusion coefficients of each component of the fluid.     

基于三维荧光光谱-平行因子分析的海上溢油识别技术研究

在世界范围内溢油事件频繁发生,溢油的组成成分会影响人类身体健康和生态系统。因此,迫切地需要一种可以快速识别溢油种类的方法。针对溢油污染物现场快速鉴别的需求,利用平行因子分析技术建立了基于三维荧光光谱的原油、燃料油识别方法。首先,利用Delannay三角形内插值法对实验选的6种原油(Roncador原油、巴士拉原油、俄罗斯原油、沙特原油(重质)、上扎库姆原油、海二站原油)和三种燃料油(380CST燃料油、5-7号燃料油、岚山燃料油)的三维荧光光谱去散射,去散射后的三维光谱数据进行归一化处理;之后,对三维荧光光谱进行平行因子解析,确定七个荧光组分为最佳荧光组分,进而得到由7个荧光成分组成的样品荧光特征谱,将风化第3,15和45天的样品及未风化样品的第一平行样的荧光特征谱进行贝叶斯方法(Bayes)判别分析和聚类分析,确定油品荧光特征谱的分析能力和18条荧光标准谱库(12条原油标准谱和6条燃料油标准谱);最后,利用非负最小二乘多元线性回归建立溢油荧光识别方法,对第0,7和30天风化的样品和未风化样品的另一平行样进行识别。实验结果表明,除对风化及未风化的俄罗斯原油识别外,该方法对其余风化和未风化的五种原油和三种燃料油识别正确率均为100.0%,整体识别原油正确率为87.5%,燃料油正确率为100.0%。     

Research on the electrostatic properties of liquid dielectric mixtures

This paper presents research results, which confirm the possibility of influencing the electrostatic charge tendency (ECT) of selected mixtures of purely insulating liquids. Tests were performed in a spinning disk system, where the factors influencing the value of the electrification current consisted of variable composition of the toluene–cyclohexane mixture, rotational speed, and a disk diameter. Liquid hydrocarbon mixtures displayed changes in ECT as well as classic insulation parameters such as resistivity and relative permittivity for concentration changes of the admixtures. These results can be used to assist the search for inhibitors of ECT and of aging processes in insulating oils.     

Statistics of defect motion in spatiotemporal chaos in inclined layer convection

We report experiments on defect-tracking in the state of undulation chaos observed in thermal convection of an inclined fluid layer. We characterize the ensemble of defect trajectories according to their velocities, relative positions, diffusion, and gain and loss rates. In particular, the defects exhibit incidents of rapid transverse motion which result in power law distributions for a number of quantitative measures. We examine connections between this behavior and Levy flights and anomalous diffusion. In addition, we describe time-reversal and system size invariance for defect creation and annihilation rates.     

The notion of persistence applied to breathers in thermal equilibrium

We study the thermal equilibrium of nonlinear Klein-Gordon chains at the limit of small coupling (anticontinuum limit). We show that the persistence distribution associated to the local energy density is a useful tool to study the statistical distribution of the so-called thermal breathers, mainly when the equilibrium is characterized by long-lived pinned excitations; in that case, the distribution of persistence intervals turns out to be a power law. We demonstrate also that this generic behaviour has a counterpart in the power spectra, where the high-frequencies domains nicely collapse if properly rescaled. These results are also compared to nonlinear Klein-Gordon chains with a soft nonlinearity, for which the thermal breathers are rather mobile entities. Finally, we discuss the possibility of a breather-induced anomalous diffusion law, and show that despite a strong slowing down of the energy diffusion, there are numerical evidences for a normal asymptotic diffusion mechanism, but with exceptionally small diffusion coefficients.     

Integration of rotational algorithms into dissipative particle dynamics: modeling polyaromatic hydrocarbons on the meso-scale

Heavy crude oil consists of thousands of compounds, a significant fraction of which have fairly large molecular weights and complex structures. Our work aims at constructing a meso-scale platform to explore this complex fluid in terms of microstructure, phase behavior, stability and rheology. In the present study, we focus on the treatment of the structures of fused aromatic rings as rigid body fragments in fractions such as asphaltenes and resins. To derive the rotational motion of rigid bodies in a non-conservative force field, we conduct a comparison of three rigid body rotational algorithms integrated into a standard dissipative particle dynamics (DPD) simulation. The simulation results confirm the superiority of the Quaternion method. To ease any doubt concerning the introduction of rigid bodies into DPD, the performance of the Quaternion method was tested carefully. Finally, the aggregation dynamics of asphaltene in very diluted toluene was investigated. The nanoaggregates are found to experience forming, breaking up and reforming. The sizes of the asphaltene monomer and nanoaggregate are identified. The diffusion coefficient of diluted asphaltene in toluene is similar to that found experimentally. All these results verify the rotational algorithm and encourage us to extend this platform to study the rheological and colloidal characteristics of heavy crude oils in the future.     

Effects of imperfect premixing coupled with hydrodynamic instability on flame propagation

The problem of flame propagation in imperfectly premixed mixtures—mixtures of reactants with variable composition—is considered in this numerical study. We carry out two-dimensional direct numerical simulations of a flame propagating in a globally lean fuel-oxidizer mixture with imposed velocity and composition fluctuations of various intensities. The configuration adopted is that of a flame front interacting with spatially evolving fluctuations, and the characteristic scales of the domain and of the fluctuations imposed are significantly larger than the characteristic thickness of the flame, to account for important flame dynamics such as the hydrodynamic instability. One-step chemistry and Fick’s diffusion law are considered, along with unity Lewis number assumption for all the species. It is observed, in agreement with previous results, that relatively weak fluctuations in composition alone may lead to a large increase in flame length and burning rate. The hydrodynamic instability caused by gas expansion, catalyzed by the composition fluctuations interacting with the flame, is found to be responsible for the flame length enhancement. It is observed as well that the relative importance of this effect diminishes as the velocity fluctuations present become more intense, and that composition fluctuations have a small impact on flame length for these cases. It is additionally found that, with increasing intensity of composition fluctuations, there is eventually a reduction of burning rate per unit length of flame which leads, consequently, to a weak reduction of overall burning rate for the largest velocity fluctuation intensities covered by this study.     

Non-Gaussian fluctuations resulting from power-law trapping in a lipid bilayer

Anomalous diffusion in lipid bilayers is usually attributed to viscoelastic behavior. We compute the scaling exponent of relative fluctuations of the time-averaged mean square displacement in a lipid bilayer, by using a molecular dynamics simulation. According to the continuous time random walk theory, this exponent indicates non-Gaussian behavior caused by a power-law trapping time. Our results provide the first evidence that a lipid bilayer has not only viscoelastic properties but also trapping times distributed according to a power law.     

From diffusion to anomalous diffusion: a century after Einstein's Brownian motion

Einstein's explanation of Brownian motion provided one of the cornerstones which underlie the modern approaches to stochastic processes. His approach is based on a random walk picture and is valid for Markovian processes lacking long-term memory. The coarse-grained behavior of such processes is described by the diffusion equation. However, many natural processes do not possess the Markovian property and exhibit anomalous diffusion. We consider here the case of subdiffusive processes, which correspond to continuous-time random walks in which the waiting time for a step is given by a probability distribution with a diverging mean value. Such a process can be considered as a process subordinated to normal diffusion under operational time which depends on this pathological waiting-time distribution. We derive two different but equivalent forms of kinetic equations, which reduce to known fractional diffusion or Fokker-Planck equations for waiting-time distributions following a power law. For waiting time distributions which are not pure power laws one or the other form of the kinetic equation is advantageous, depending on whether the process slows down or accelerates in the course of time.