Experimental study of asphaltene deposition in transparent microchannels using the light absorption method

This study focuses on an experimental investigation of asphaltene deposition in a vertical transparent microchannel. Heptane-induced asphaltene precipitation is utilized to precipitate dissolved asphaltene in crude oil into asphaltene particles at ambient temperature and standard atmospheric pressure. These asphaltene particles deposit gradually on the surface of microchannels. The key parameters that influence the mechanism of asphaltene deposition are the ratio of crude oil to n-heptane and experimental elapsed time. At a constant flowrate, the amount of asphaltene deposited on a transparent channel wall is quantified using a new flow visualization technique based on reflected light intensity and image analysis. Asphaltene precipitation and deposition strongly affect the reflected light intensity through the change of mixture color in the recorded images. Experimental results show that asphaltene deposition process follows three stages, (i) slow asphaltene particle deposition at the beginning of the experiment, (ii) a rapid and continuous deposition occurring after few hours and (iii) a slower deposition (decreasing deposition rate) at the end of the experimentation. The experimental results for different crude oil to n-heptane ratios illustrate that deposition increases with this ratio, i.e. increasing concentration of n-heptane. An empirical equation is developed to correlate the intensity of the light absorption to the thickness of the deposited asphaltene in a transparent microchannel. Non-uniform deposition along the longitudinal direction of the microchannel is characterized. Deposits decrease with increasing longitudinal distance from the inlet. This non-uniform deposition distribution is due to local mass transport limitations and asphaltene aggregation size effect.     

Characterization of a heavy oil–propane system in the presence or absence of asphaltene precipitation

When a light hydrocarbon solvent is injected into a heavy oil reservoir under a sufficiently high reservoir pressure, asphaltene precipitation occurs so that the heavy oil is in situ deasphalted during a hydrocarbon solvent-based heavy oil recovery process. The physicochemical properties of this in situ deasphalted heavy oil are rather different from those of the original crude oil in the heavy oil reservoir. In this paper, a heavy oil sample is saturated with a typical light hydrocarbon solvent (i.e., propane) under different saturation pressures in a see-through windowed high-pressure saturation cell. The heavy oil–propane system is characterized by measuring and comparing several important physicochemical properties of the propane-saturated heavy oil samples under different saturation pressures and the flashed-off heavy oil samples, such as the solubility, oil-swelling factor, density, viscosity, asphaltene content, hydrogen and carbon aromaticities. When the heavy oil is saturated with propane at P ≤ 780 kPa and T = 20.8 °C, there is no observable asphaltene precipitation and deposition under a microscope camera. The respective properties of the propane-saturated heavy oil samples taken from the upper and lower parts of the saturation cell are measured and found to be essentially the same within the experimental errors so that the entire system is considered to be almost homogeneous. If the saturation pressure is increased to P = 850 kPa, strong asphaltene precipitation occurs and some large asphaltene particles are deposited onto the bottom of the saturation cell. In this case, the heavy oil is deasphalted and the flashed-off heavy oil has lower density, viscosity, asphaltene content, hydrogen and carbon aromaticities than those of the original heavy crude oil.     

Experimental and modeling studies on the asphaltene precipitation in degassed and gas-injected reservoir oils

The asphaltene precipitation in a Chinese crude oil has been studied experimentally under normal-pressure and high-pressure conditions. The onset of asphaltene precipitation was detected by using light transmission method. Normal pentane and hexane were used as precipitating agents for studying the onset of asphaltene deposition in (asphaltene+toluene) and (degassed crude oil+toluene) mixtures under normal pressure. A total of eighteen sets of normal pressure data have been measured. For high-pressure gas-injected reservoir oil systems, the effects of injection-gas concentration, temperature, pressure, and the presence of a coexisting aqueous electrolyte (brine) phase on the amount of asphaltene deposition were studied and a total of seven sets of data have been measured. In the modeling part, a modified Hirschberg solubility model and a new solubility parameter correlation were proposed. The model parameters determined from low-pressure precipitation data have been successfully extended to high-pressure systems. Extensive tests vs. the data measured in this work and literature data show that the proposed model is capable of giving reasonable calculation results for most cases.     

A comparative study to evaluate the performance of coated Fe3O4 nanoparticles for adsorption of asphaltene from crude oil in bench scale

The present study was conducted to evaluate the performance of magnetic Fe₃O₄ nanoparticles coated with polythiophene (PT), Mil-101 (Cr) (MOF), graphene oxide (GO), SiO₂, and chitosan for adsorption of asphaltene from crude oil in a bench scale setup. All nanoparticles were synthesized using co-precipitation method. The characteristics of nanoparticles were verified using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and field emission scanning electron microscope (FESEM) analyses. The concentration of nanoparticles was kept constant at the optimum value of 10g?L^?1. The amount of asphaltene adsorption was determined at different contact times of 0.5, 0.75, 1, 2, and 4 hours. The results showed that the adsorption increased with contact time and reached equilibrium after about 2 hours in both continuous and batch experiments. The amount of asphaltene adsorption was lower in continuous experiments compared to batch experiments. However, it was found that magnetic nanoparticles are applicable for inhibition of asphaltene precipitation under flow conditions. Furthermore, polythiophene coating on magnetic Fe₃O₄ nanoparticles had the highest capacity for asphaltene adsorption. Besides, by applying a magnetic field, the magnetic nanoparticles that adsorbed asphaltene can be separated from crude oil to prevent asphaltene aggregation and precipitation.     

Developing Thermodynamic Micellization Approach to Model Asphaltene Precipitation Behavior

An little known yet significant issue in petroleum production processes in petroleum reservoirs is asphaltene precipitation/deposition. Asphaltene has not only a fuzzy and vague nature but it also can cause detrimental problems like reservoir blockage and, as a result, low oil recovery. To tackle this issue, many researchers have attempted to monitor asphaltene behavior versus thermodynamic conditions. A thermodynamic micellization approach is implemented in this work to describe asphaltene precipitation behavior for two sample fluids from Iranian reservoirs. First, the basic structures of the addressed approach and different contributions to Gibbs free energy of micellization proposed by Victorov and Firoozabadi (VF) are demonstrated. Second, a detailed sensitivity analysis with respect to the model parameters is performed by utilizing a new calculation strategy. Finally, a comparison between the predicted precipitation curve and the experimental one is illustrated; moreover, comparing our results with those reported by Victorov proves the superiority of the new strategy over the conventional one. The significance of this study shows the effect of each micellization parameter on the asphaltene precipitation behavior curve and illustrates the ability of the micellization approach evolved by VF in monitoring the effect of pressure on asphaltene precipitation using the new calculation procedure. Outcomes from this study could couple with commercial reservoir simulation software to improve precision and integrity for designing robust and effective production units.     

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.      

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.     

Understanding the fluid phase behaviour of crude oil: Asphaltene precipitation

We present a simplified but consistent picture of asphaltene precipitation from crude oil from a thermodynamic perspective, illustrating its relationship to the familiar bubble curve via the calculation of constant-composition p-T phase diagrams that incorporate both the bubble curve and the asphaltene precipitation boundary. Using the statistical associating fluid theory (SAFT) we show that the position of the precipitation boundary can be explained using a very simple fluid model including relatively few components. Our results support the view that the precursor to asphaltene precipitation is a liquid-liquid phase separation due to a demixing instability in the fluid. Moreover, the bubble curve for these systems is seen to represent a boundary between regions of two-phase (liquid-liquid) and three-phase (vapour-liquid-liquid) equilibria.     

Experimental Evaluation of the Additive Compounds Performance on Asphaltene Precipitation Using Automatic Titration Method

The use of soluble amphiphiles oil types provide the most practical and economical solution for crude oil treatment in order to control the asphaltene precipitation phenomenon. In this article, the inhibition performance of a number of new chemical additives to asphaltene precipitation is examined on two types of Iranian crude oil. An automatic titration method is used in experimental evaluation. The vegetable oil types (hazelnut, wheat germ, and walnut), organic acids (oleic and linoleic) and chemical additives (4-dodecylresorcinol and benzyl alcohol) displayed the highest capacity to inhibit asphaltene precipitation. A remarkable onset displacement is displayed by dodecyl resorcinol. The results also revealed that the vegetable oil have high potential in delaying asphaltene precipitation.     

Model molecules mimicking asphaltenes

Asphalthenes are typically defined as the fraction of petroleum insoluble in n-alkanes (typically heptane, but also hexane or pentane) but soluble in toluene. This fraction causes problems of emulsion formation and deposition/precipitation during crude oil production, processing and transport. From the definition it follows that asphaltenes are not a homogeneous fraction but is composed of molecules polydisperse in molecular weight, structure and functionalities. Their complexity makes the understanding of their properties difficult. Proper model molecules with well-defined structures which can resemble the properties of real asphaltenes can help to improve this understanding. Over the last ten years different research groups have proposed different asphaltene model molecules and studied them to determine how well they can mimic the properties of asphaltenes and determine the mechanisms behind the properties of asphaltenes.     

Effect of low-salinity water on asphaltene precipitation

The effect of low-salinity (1000 to 5000?ppm) and intermediate-salinity (5000 to 40000?ppm) water (MgSO₄, MgCl₂, Na₂SO₄, CaCl₂, NaCl and KCl) on asphaltene precipitation was investigated in this work. The results revealed that all brines intensify the amount of asphaltene precipitation. All cases exhibited initial downward trend followed by the upward trend for the amount of asphaltene precipitation with increasing the brine concentration. A similar trend was also observed for Interfacial Tension (IFT) between crude oil and brine in this study. IFT was tested for MgSO₄, MgCl₂, Na₂SO₄, CaCl₂, NaCl and KCl brines with concentrations of 1000 to 40000?ppm. Finally, experimental results showed that an increase in volume of all brines in the mixture (brine +oil) led to increase and decrease of the asphaltene precipitation in low and intermediate salinity regions, respectively.     

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.     

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.     

Influence of Asphaltene Concentration on the Interfacial Properties of Two Typical Demulsifiers

Oil-in-water emulsion is an innovate manner by which heavy crude oil can be transported from producing sites to transforming sites through pipelines. The effect of emulsifier on the interfacial properties and demulsification performance of demulsifier for heavy crude oil–in-water emulsion has been studied by many researchers. However, the influence of asphaltene in heavy crude oil on the interfacial properties of demulsifier has not been investigated yet. In this article, the influence of asphaltene concentration of two typical demulsifiers (straight-chained SP-1 and branch-chained AE-1) was systematically studied in terms of absorption thermodynamics, absorption kinetics, and coalescence kinetics. The results revealed that the demulsifier adsorption was a ΔS controlled spontaneous process. The absolute value of ΔG of SP-1 adsorption was found to decrease with asphaltene concentration, whilst the asphaltene concentration had no significant influence on that of AE-1. With the increase of asphaltene concentration, the demulsifiers’ adsorption rates increased, but the reorganization rates on the interface decreased. Coalescence speed of asphaltene droplet decreased with asphaltene concentration in spite of demulsifier type. Additionally, AE-1 had higher absolute value of ΔG, adsorption speed, and coalescence speed than that of SP-1 at the same condition.     

Circular dichroism of crude oil and its derivatives. Role of permolecular structures

Petrols with different octane numbers, diesel fuel and solutions of crude oil in toluene have been studied by the methods of absorption spectroscopy, circular dichroism spectroscopy and correlation spectroscopy of scattered light. Circular dichroism signal was registered for crude oil solutions in the spectral ranges corresponding to the measured earlier resonance absorption of asphaltene solutions in toluene. We show that the optical activity of crude oil solutions is due to the aggregation of asphaltene molecules in one spectral range and is intensified with the aggregation of asphaltene molecules in another spectral range. Petrols have no optical activity. The optical activity registered for diesel fuel is possibly due to the aggregation of asphaltene molecules.     

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.     

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.     

Thermal kinetics study of light oil oxidation using TG/DTG techniques

In this study, the oxidation behavior of crude oils in the presence and absence of rock cuttings was investigated by thermogravimetry/derivative thermogravimetry (TG/DTG) techniques. Prior to these tests, the composition of cuttings and properties of crude oils were analyzed. Three obvious reaction regions were observed from the TG/DTG curves which are recognized as low-temperature oxidation (LTO), fuel deposition (FD), and high-temperature oxidation. The effects of light components (C_7–15), heavy fractions (asphaltene, paraffin, resin), and cutting on oil oxidation behavior were analyzed. Kinetic analysis of crude oils and oil + cutting mixtures was performed by Arrhenius method, and the data were analyzed at last. Results show that high content C_7–15 hydrocarbons can provide negative effect on the LTO behavior of crude oil. On the contrary, the high content unsaturated heavy hydrocarbons including asphaltene, paraffin, and resin are benefit for the oxidation performance. In addition, a shortened FD stage and higher peak temperature in LTO region are observed by addition of cutting. Cutting especially clay in it plays an active role of catalyzing in oil oxidation reaction.     

生物降解原油研究的新方法

利用沥青质包裹烃和沥青质钌离子催化氧化（RICO）产物中的生标对生物降解原油进行了研究。研究表明，虽然原油中的生标受到了严重破坏，但利用这两种方法在沥青质中均可以获得较为完整的生标系列。与其它方法相比，这两种方法简单方便，结果较为可靠、准确，可能是生物降解原油研究的发展方向。