Intermolecular Magnetic Spin–Spin Interactions in Solution State at 1.53 mT

Overhauser dynamic nuclear polarization (DNP) technique can provide a dramatic increase in the signal obtained from nuclear magnetic resonance experiments owing to the magnetic spin–spin interactions between ¹H nuclei of the solvent and electrons delocalized on the asphaltene in crude petroleum or asphalt. Studies on ¹H Overhauser DNP enhancements at 1.53 mT are reported for benzene solvent medium with three different radical sources: Iran crude petroleum, MC30 liquid asphalt, and MC800 liquid asphalt for a range of radical concentrations. The results show that protons of benzene are good detectors for dipolar coupling.     

X‐Band DNP Hyperpolarization of Viscous Liquids and Polymer Melts

NMR studies of synthetic polymers and biomacromolecules, which provide insight into the conformation and dynamics of these materials, can benefit strongly from the increased sensitivity offered by dynamic nuclear polarization (DNP) and other hyperpolarizing methods. In this study ¹H DNP nuclear spin hyperpolarization of two polybutadiene samples, representing a supercooled liquid and an entangled polymer melt, is demonstrated at 0.35 T magnetic field strength and at temperatures between −80 and +50 °C. Electron spin polarization transfer from the α,γ‐bisdiphenylene‐β‐phenylallyl radical to the sample nuclei is achieved by the Overhauser and solid effect. DNP signal enhancements are studied, varying the electron spin resonance offset, microwave power, and sample temperature. The influence of spin relaxation times, line widths, and molecular dynamics are discussed. The results show promising, up to 15‐fold NMR signal enhancements using noncryogenic temperatures and an inexpensive setup that is less technically demanding than current high‐field DNP setups.

     

Morphology and Size Distribution Characterization of Precipitated Asphaltene from Live Oil During Pressure Depletion

The size and morphology of asphaltene aggregates, precipitated from live oil by pressure depletion at the reservoir temperature was studied using scanning electron microscopy and atomic force microscopy. The experimental studies showed that the mean size of aggregates increased when pressure decreased. The results indicate that the morphology of aggregates was changed from amorphous spherical and elliptical shapes to irregular. A bimodal distribution function was able to describe the size distribution in pressure range of 500 to 3500 psi. At higher pressure, the unimodel was able to represent the size distribution. The results showed reduction in live oil stability and asphaltene aggregation with pressure drop.     

Evaluation of Asphaltene Inhibitors Effect on Aggregation Coupled Sedimentation Process

The aggregation coupled sedimentation of asphaltene particles in toluene and heptanes mixture are investigated in the presence of two asphaltene inhibitors including, dodecyle resorcinol (DR) and hazelnut oil. An image processing technique is adopted in the three sections in a settling column setup. The aggregation and sedimentation phenomena are evaluated through a time-driven Monte Carlo (MC) model. The results are in good agreement with the obtained experimental results. The results indicate that in controlling asphaltene sedimentation DR is more effective. The results also revealed that the hazelnut oil has a capacity to inhibit asphaltene sedimentation at high concentration.     

DNP sensitivity of 19F‐NMR signals in hexafluorobenzene depending on polarizing agent type

Low field dynamic nuclear polarization or low field magnetic double resonance technique enables enhanced nuclear magnetic resonance signals to be detected without increasing the strength of the polarizing field. The study reports that the dynamic nuclear polarization of ¹⁹F nuclei in hexafluorobenzene solutions doped with nitroxide, BDPA, MC800 asphaltene and MC30 asphaltene free radicals at 15 G. The ¹⁹F nuclei in all solutions gave positive DNP enhancements changing between 3.42 and 189.54, corresponding to predominantly scalar interactions with the unpaired electrons in the radicals. DNP sensitivity of ¹⁹F nuclei in hexafluorobenzene was observed to be changed significantly depending on the radical type. Nitroxide was found to have the best DNP performance among the polarizing agents. Copyright © 2016 John Wiley & Sons, Ltd.     

Experimental Investigation of the Effects of Different Parameters on the Rate of Asphaltene Deposition in Laminar Flow and Its Prediction Using Heat Transfer Approach

In this study, asphaltene deposition from crude oil on the pipe surface has been studied experimentally using a novel designed test loop. Washing technique is used to quantitatively measure the rate of asphaltene deposition during laminar flow in the steel pipe. The effects of oil velocity, asphaltene content, and surface temperature on the thickness of asphaltene deposition are investigated. The results show that the asphaltene deposition rate increases with increasing surface temperature, results in asphaltene content reduction of the flowing crude oil. As the oil velocity increases, less deposition was noticed on the surface of the pipe. Besides, thermal approach was applied to the experimental procedure which shows good agreements between the predicted thickness and the measured value from the test loop.     

Investigation of Asphaltene Aggregate Size Distribution Under Aggregation and Breakage Phenomena Using Monte Carlo Simulation

In this article, the aggregation and breakage processes are simulated through Monte Carlo method for asphaltene aggregates under shear-induced petroleum mixtures. The simulation results are verified by the aggregate size distributions of two types of asphaltenes having different fractal dimensions extracted from Iranian crude oil types. The obtained aggregate size distributions are affected by shear rate, toluene to heptane ratios and the oil type. The dynamic evolution of asphaltene aggregates shows an ascendant trend with time until they reach a maximum average diameter and then descent to a steady-state size. The asphaltene fractal dimension affects the aggregation process.     

Generation of Asphaltene Deposition Envelope Using Artificial Neural Network

The usefulness of the asphaltene deposition envelope (ADE) is that no asphaltene flocculation occurs at conditions outside the envelope. Since artificial neural network (ANN) is best at identifying patterns or trends in data, it is well suited for prediction or forecasting needs. ANN is also capable of addressing case specific problems that may be encountered in the field such as deposition of asphaltene. In this article, the high pressure, high temperature setup used to perform pressure depletion experiments at three different temperatures on one the Iranian live oils and the ADE generated using ANN.     

Investigation of Oil–Asphaltene Slurry Rheological Behavior

The presence of asphaltene means additional difficulties related to transport and processing due to the increased crude oil viscosity caused by the asphaltene. For a better knowledge of the flow properties of asphaltene containing crude oils, it is necessary to understand how asphaltene affects the rheological properties. The aim of this article is to provide information on such rheological properties of oil–asphaltene slurry systems. The results of rheological experiments show that the non-Newtonian flow curves can be approximated by the Bingham plastic model to determine the apparent viscosity and the yield stress as a function of asphaltene concentration and temperature. An explanation is also provided for the observed behavior.     

Asphaltene Instability Trends of Light and Heavy Crude Oils

In this work, two Iranian crude oils diluted in 1-methylnaphthalene (1-MN) were titrated with selected n-alkanes. Subsequently, samples were observed microscopically to determine the onset of asphaltene precipitation. A series of micrographs from de-asphaltening were used to show visible changes of the asphaltene sizes, shapes, and frequencies by addition the n-heptane to the subsamples after 5, 6, 11, and 24 hour lag times. The refractive indices (RI) of the titrated mixtures at different temperatures below and above the onset conditions were measured aiming to establish the asphaltene instability trend. Results show that for the diluted light and heavy crude oils, the onset of asphaltene precipitation is rather a gradual process with an almost constant slope of RI decrease due to the separation of asphaltene clusters from the mixture. This is a kinetically controlled process. Furthermore, the nature of the precipitant is likely to play a notable role. The rate of RI decreasing with temperature was approximately 0.0004/°C for both tested crude oils.     

Smart Determination of Difference Index for Asphaltene Stability Evaluation

Precipitation and deposition of asphaltene during different stages of petroleum production is recognized as problematic in oil industry because of the increase in production cost and the inhibition of a consistent flow of crude oil in different medium. Numerous correlations have been developed to determine asphaltene stability in crude oil. In this study, a novel ONN method was used to estimate difference index from SARA fraction data for rapid, accurate, and cost-effective determination of asphaltene stability. Neural networks are highly in danger of trapping in local minima. To eliminate this flaw, a hybrid genetic algorithm-pattern search technique was used instead of common back-propagation algorithm for training the employed neural network. A comparison between neural network and optimized neural network indicated superiority of optimized neural network.      

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.     

Fuzzy Assessment of Asphaltene Stability in Crude Oils

Knowledge about stability of asphaltene, determined by difference index, is of significant interest because of the many problems associated with asphaltene precipitation. This study followed two parallel fuzzy strategies for estimating refractive index (RI) of crude oil and refractive index of crude oil at onset of asphaltene precipitation (PRI) from Sara fraction data. Predicted RI and PRI were then utilized for easy and fast diagnosis of asphaltene stability by dint of calculating difference index (or ΔRI = RI – PRI). The experimental data reported in the literature have been used for model developing and checking. An acceptable agreement between fuzzy predicted values and experimental data confirmed the power of fuzzy logic technique in prediction of RI, PRI, and consequent ΔRI. In this study, ΔRI was not predicted directly mainly for two reasons. First, RI and PRI contain invaluable information themselves and predicting them fulfills the need for these information when they are desired. Second, dividing the problem into two simpler parts and solving them separately enhances the terminal accuracy of prediction. Although the regression accuracy for ΔRI was not completely satisfied, the classification accuracy for discriminating between stable and unstable situations was 100%.      

Synthesis of AA-MMA Block Copolymer by RAFT Polymerization and Used as Emulsifier cum Macroinitiator and Its Influence on the Film Properties

Blocked copolymer of acrylic acid-methyl methacrylate with controlled molecular architecture were prepared by reversible addition chain fragmentation polymerization and were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (¹H NMR), and gel permeation chromatography (GPC) for structural evaluation. The neutralized copolymers were evaluated for the critical micelle concentration (CMC), hydrophilic lipophilic balance (HLB) and were utilized as polymeric emulsifier cum macro RAFT initiator for the synthesis of acrylic binder. The structure properties of the emulsifier were evaluated correlating with the film properties.