Probing the interaction between asphaltene-wax and its effects on the crystallization behavior of waxes in heavy oil via molecular dynamics simulation

High content of asphaltenes and waxes leads to the high pour point and the poor flowability of heavy oil,which is adverse to its efficient development and its transportation in pipe.Understanding the interaction mechanism between asphaltene-wax is crucial to solve these problems,but it is still unclear.In this paper,molecular dynamics simulation was used to investigate the interaction between asphaltenewax and its effects on the crystallization behavior of waxes in heavy oil.Results show that molecules in pure wax are arranged in a paralleled geometry.But wax molecules in heavy oil,which are close to the surface of asphaltene aggregates,are bent and arranged irregularly.When the mass fraction of asphaltenes in asphaltene-wax system(ω_(asp))is 0-25 wt%,the attraction among wax molecules decreases and the bend degree of wax molecules increases with the increase ofω_(asp).Theω_(asp)increases from 0 to 25 wt%,and the attraction between asphaltene-wax is stronger than that among waxes.This causes that the wax precipitation point changes from 353 to 333 K.While theω_(asp)increases to 50 wt%,wax molecules are more dispersed owing to the steric hindrance of asphaltene aggregates,and the interaction among wax molecules transforms from attraction to repulsion.It causes that the ordered crystal structure of waxes can't be formed at normal temperature.Simultaneously,the asphaltene,with the higher molecular weight or the more hetero atoms,has more obvious inhibition to the formation of wax crystals.Besides,resins also have an obvious inhibition on the wax crystal due to the formation of asphalteneresin aggregates with a larger radius.Our results reveal the interaction mechanism between asphaltene-wax,and provide useful guidelines for the development of heavy oil.

Numerical Simulation of Asphaltene Precipitation and Deposition during Natural Gas and CO_(2) Injection

Asphaltene deposition is a significant problem during gas injection processes,as it can block the porous medium,the wellbore,and the involved facilities,significantly impacting reservoir productivity and ultimate oil recovery.Only a few studies have investigated the numerical modeling of this potential effect in porous media.This study focuses on asphaltene deposition due to natural gas and CO_(2) injection.Predictions of the effect of gas injection on asphaltene deposition behavior have been made using a 3D numerical simulation model.The results indicate that the injection of natural gas exacerbates asphaltene deposition,leading to a significant reduction in permeability near the injection well and throughout the reservoir.This reduction in permeability strongly affects the ability of gas toflow through the reservoir,resulting in an improvement of the displacement front.The displacement effi-ciency of the injection gas process increases by up to 1.40%when gas is injected at 5500 psi,compared to the scenario where the asphaltene model is not considered.CO_(2) injection leads to a miscible process with crude oil,extracting light and intermediate components,which intensifies asphaltene precipitation and increases the viscosity of the remaining crude oil,ultimately reducing the recovery rate.

Experimental investigation of the effects of oil asphaltene content on CO_(2) foam stability in the presence of nanoparticles and sodium dodecyl sulfate

Foam stability tests were performed using sodium dodecyl sulfate(SDS)surfactant and SiO2 nanoparticles as foaming system at different asphaltene concentrations,and the half-life of CO_(2) foam was measured.The mechanism of foam stability reduction in the presence of asphaltene was analyzed by scanning electron microscope(SEM),UV adsorption spectrophotometric concentration measurement and Zeta potential measurement.When the mass ratio of synthetic oil to foam-formation suspension was 1:9 and the asphaltene mass fraction increased from 0 to 15%,the half-life of SDS-stabilized foams decreased from 751 s to 239 s,and the half-life of SDS/silica-stabilized foams decreased from 912 s to 298 s.When the mass ratio of synthetic oil to foam-formation suspension was 2:8 and the asphaltene mass fraction increased from 0 to 15%,the half-life of SDS-stabilized foams decreased from 526 s to 171 s,and the half-life of SDS/silica-stabilized foams decreased from 660 s to 205 s.In addition,due to asphaltene-SDS/silica interaction in the aqueous phase,the absolute value of Zeta potential decreases,and the surface charges of particles reduce,leading to the reduction of repulsive forces between two interfaces of thin liquid film,which in turn,damages the foam stability.

The deposition of asphaltenes under high-temperature and highpressure (HTHP) conditions

In this work,the factors affecting asphaltenes deposition in high-temperature and high-pressure wells were studied using backscattered light and PVT equipment customized to suit the well conditions.In an examination of the intensity of backscattered light,it was revealed that there exists a linear relationship between temperature and asphaltene precipitation within a specific temperature range.Within this range,a decrease in temperature tends to accelerate asphaltene precipitation.However,the impacts of pressure and gas-oil ratio are more pronounced.The pressure depletion induces the asphaltenes to precipitate out of the solution,followed by the formation of flocs below the bubble point.In addition,an increase in the gas-oil ratio causes a more severe asphaltene deposition,shifting the location of asphaltenes to deep well sections.

Effect of existence state of asphaltenes on the asphaltenes-wax interaction in wax deposition

Asphaltenes are the most elusive substances in waxy crude oil,especially the complex structures,which leads to significant precipitation and aggregation characteristics of asphaltenes,and affects the asphaltenes-wax interaction.In this study,the concept of the existence state of asphaltenes was introduced to semi-quantitatively investigate the precipitation and aggregation characteristics of asphaltenes.On this basis,the influence of the existence state of asphaltenes on wax deposition was studied by coldfinger device and high-temperature gas chromatography,and the composition and properties of the deposits were analyzed.Four main findings were made:(1)As the asphaltene concentration increases,the existence state of asphaltenes gradually transitions from dispersed state to aggregated state,and the asphaltene concentration of 0.30 wt%in this study is the starting point of the transition.(2)The existence state of asphaltenes in crude oil does affect the process of wax deposition,as shown in the fact that the dispersed asphaltenes promote the occurrence of wax deposition,while the aggregated asphaltenes can inhibit wax deposition.(3)In the presence of the aggregated asphaltenes,that is,when the asphaltene concentration is higher than 0.30 wt%,the shedding phenomenon of deposit layer was observed,and with the increase of aggregated asphaltenes,the deposit layer fell off earlier.(4)With the increase of the dispersed asphaltenes,the wax appearance temperature(WAT)and wax content of the deposits all showed an increasing trend,while with the appearance of the aggregated asphaltenes,the above situation was reversed.The findings of this study can help for better understanding of the interaction between the asphaltenes and wax in wax deposition.

The influence of composition of asphaltenes of different genesis on the properties of carbon materials manufactured from them by plasma processing

The results of experimental studies of carbon materials, which are formed in the plasma of a direct current (DC) arc discharge initiated in open air from the asphaltenes of different origins, extracted from the natural asphaltite and from the oil of the Sredne-Ugutskoye Oilfield, are presented. The influence of the initial asphaltene composition on the composition and properties of the resulting carbon materials is analyzed. The initial asphaltenes and the samples of the carbon materials are characterized by the methods of X-ray diffraction, differential thermal analysis, X-ray fluorescence analysis, IR-Fourier spectroscopy, laser diffraction, transmission and scanning electron microscopy. The changes in the composition and structure of the asphaltenes are determined before and after their plasma treatment and the hypotheses are put forward concerning the chemical processes causing the changes in the molecular structure of the samples. As a result of plasma treatment of asphaltenes (100 A, 30 s), it was shown that graphitization occurs, as well as oxidation, and a decrease in sulfur content. Moreover, nanotubes and nano-onions have been detected using electron microscopy. Petroleum asphaltenes after plasma treatment give a less thermostable carbon material, but with a lower content of heteroatoms, and with a large amount of sulfur in the composition of sulfoxide structural fragments. This method is shown to be a promising technology for processing the petroleum feedstock enriched with heavy asphaltene components for the manufacture of carbon nanomaterials: nanotubes, nano-onions and polyhedral graphite.

Change of asphaltene and resin properties after catalytic aquathermolysis

Resin and asphaltene were separated from Liaohe heavy oil. Catalytic aquathermolysis of asphaltene and resin was investigated by using water soluble catalysts （NiSO4 and FeSO4） and oil soluble catalysts （nickel naphthenate and iron naphthenate）. Before and after aquathermolysis, the properties of the resin and asphaltene was compared by means of ultimate analysis, vapor pressure osmometer （VPO） average molecular weight, X-ray diffraction （XRD）,^13C and ^1H nuclear magnetic resonance （NMR）. The conversion sequence was as follows： No-catalyst〈NiSO4〈FeSO4〈nickel naphthenate〈iron naphthenate. In the presence of catalysts, the amount of H2 and CO increased significantly, while H2S in the gas product decreased. The molecular weight of asphaltene and resin increased after reaction without catalyst. But the catalysts restrained this trend. The H/C ratio of asphaltene and resin decreased after reaction. From the results of average structural parameters and molecular weight, it was found that asphaltene and resin were partly aggregated after aquathermolysis.

Asphaltenes: Separations, structural analysis and applications

Asphaltenes, complex aromatic compounds from various carbonaceous sources, could be obtained by solvent dissolution, filtration and adsorption. It was difficult to clarify the molecular structures and chemical properties of asphaltene due to its structural similarity, composition complexity and source dependences. Many techniques, like Mass spectrometry, Chromatography, Nuclear magnetic resonance spectroscopy, Infrared spectroscopy, Roman spectroscopy, Fluorescence spectroscopy, X-ray diffraction analysis and Small-angle scattering techniques and so on, have revealed some valuable descriptions of asphaltenes chemical compositions and fundamental structures. Moreover, advanced Mass spectrometry,Atomic force microscopy and Scanning tunneling microscopy could provide more clear and essential molecular compounds and structures in asphaltenes. In addition, several asphaltenes models have succeeded to illustrate aggregation properties asphaltene. In this work, the progress on asphaltene separation, characterization and application was summarized, and the similarities and differences between coal-derived asphaltenes and petroleum asphaltenes were compared. Furthermore, the reactivity of asphaltenes has been discussed in the aspect of hydroprocessing, pyrolysis and gasification. Asphaltene was excellent carbon precursor for functional carbon material due to its high aromaticity and carbon yield;several porous carbon nanosheets from asphaltenes that would be prospective electrode materials after being graphitized were shown. Pitch-based carbon fiber derived from coal-derived asphaltenes displayed a tensile strength of 1.0 GPa and elastic modulus of 350 MPa, respectively. These powerful advances will provide asphaltenes promising developments.

A comprehensive experimental evaluation of asphaltene dispersants for injection under reservoir conditions

As the efficiency of dispersants with different origins is questionable for each typical oil sample, the present study provides a reproducible and reliable method for screening asphaltene dispersants for a typical asphal- tenic crude oil. Four different asphaltene dispersants （polyisobutylene succinimide, polyisobutylene succinic ester, nonylphenol-formaldehyde resin modified by polyamines, and rapeseed oil amide） were prepared and their performance on two oils from an Iranian field under laboratory and reservoir conditions was studied. A thorough analysis including ash content and SARA tests was performed on the solid asphaltene particles to characterize the nature of deposits. Then a highly efficient carrier fluid, which is crucial when injecting dispersant into the wells, was selected from a variety of chemicals by comparing their solubility. In the next step, using an optical microscope, a viscometer, and a Turbiscan, the screening of dispersants under laboratory conditions was done on a mixture of dead oil and dispersant to evaluate the onset of asphaltene precipitation and its stability when titrating by a precipitant. Finally, two different mixtures of the efficient dispersants, live oil, and carrier fluid were used with the solid detection system （SDS） and the filtration method to examine their effects on the onset pressure of asphaltene precipitation and the asphaltene content of the crude oil under reservoir conditions. The results show that the combination of experimental methods used in this work could be consistently applied to screening asphaltene dispersants. Among the four different dispersants applied here, the dispersant based on nonylphenol-formaldehyde resin modified by polyamines showed the best performance on the available live oils. This chemical modified the onset pressure of asphaltene precipitation of light oil from 4300 psi to about 3600 psi and decreased the precipitated asphaltene of heavy oil by about 30 %.

Investigation into mechanisms and kinetics of asphaltene aggregation in toluene/n-hexane mixtures

Determining the rate of asphaltene particle growth is one of the main problems in modeling of asphaltene precipitation and deposition.In this paper,the kinetics of asphaltene aggregation under different precipitant concentrations have been studied.The image processing method was performed on the digital photographs that were taken by a microscope as a function of time to determine the asphaltene aggregation growth mechanisms.The results of image processing by MATLAB software revealed that the growth of asphaltene aggregates is strongly a function of time.Different regions could be recognized during asphaltene particle growth including reaction-and diffusion-limited aggregation followed by reaching the maximum asphaltene aggregate size and start of asphaltene settling and the final equilibrium.Modeling has been carried out to predict the growth of asphaltene particle size based on the fractal theory.General equations have been developed for kinetics of asphaltene aggregation for reaction-limited aggregation and diffusion-limited aggregation.The maximum size of asphaltene aggregates and settling time were modeled by using force balance,acting on asphaltene particles.Results of modeling show a good agreement between laboratory measurements and model calculations.

Stabilizing silica nanoparticles in high saline water by using polyvinylpyrrolidone for reduction of asphaltene precipitation damage under dynamic condition

In this study, the performance of stable nanofluid containing SiO2 nanoparticles dispersed and stabilized in high salinity brine for asphaltene inhibition in dynamic condition is evaluated. In the first stage of this work, the stability of silica nanoparticles in different range of water salinity(0–100000 mg·L-1) is investigated. Next, stable nanofluid containing highest salinity is selected as asphaltene inhibitor agent to inject into the damaged core sample. The estimated values of oil recovery for base case, after damage process and after inhibition of asphaltene precipitation using nanofluid are 51.6%, 36.1% and 46.7%, respectively. The results showed the reduction in core damage after using nanofluid. In addition, the relative permeability curves are plotted for the base case, after damage process and also after inhibition of asphaltene precipitation using nanofluid. Comparison of relative permeability curves shows, relative permeability of oil phase decreased after damage process as compared with the base case. But after using nanofluid the oil relative permeability curve has shifted to the right and effective permeability of oil phase has been improved.

Synthesis of boron, nitrogen co-doped porous carbon from asphaltene for high-performance supercapacitors

Oxidized asphaltene （OA）, a thermosetting material with plenty of functional groups, is synthesized from asphaltene （A） using HNO3]HzSO4 as the oxidizing agent. Boron, nitrogen co-doped porous carbon （BNC-OA） is prepared by carbonization of the mixture of boric acid and OA at 1173 K in an argon atmosphere. X-ray photoelectron spectroscopy （XPS） characterization reveals that the BNC-OA has a nitrogen content of 3.26 at.% and a boron content of 1.31 at.%, while its oxidation-free counterpart （BNC-SA） has a nitrogen content of 1.61 at.% and a boron content of 3.02 at.%. The specific surface area and total pore volume of BNC-OA are 1103 m2·g^-1 and 0.921 cm3·g^-1, respectively. At a current density of 0.1 A·g^-1, the specific capacitance of BNC-OA is 335 F·g^-1 and the capacitance retention can still reach 83% at 1 A·g^-1. The analysis shows that the superior electrochemical performance of the BNC-OA is attributed to the pseudocapacitance behavior of surface heteroatom functional groups and an abundant pore-structure. Boron, nitrogen co-doped porous carbon is a promising electrode material for supercapacitors.

Study of asphaltene deposition from Tahe crude oil

Borehole blockage caused by asphaltene deposition is a problem in crude oil production in the Tahe Oilfield, Xinjiang, China. This study has investigated the influences of crude oil compositions, temperature and pressure on asphaltene deposition. The asphaltene deposition trend of crude oil was studied by saturates, aromatics, resins and asphaltenes （SARA） method, and the turbidity method was applied for the first time to determine the onset of asphaltene flocculation. The results showed that the asphaltene deposition trend of crude oil by the turbidity method was in accordance with that by the SARA method. The asphaltene solubility in crude oil decreased with decreasing temperature and the amount of asphaltene deposits of T739 crude oil （from well T739, Tahe Oilfield） had a maximum value at 60℃. From the PVT results, the bubble point pressure of TH 10403CX crude oil （from well TH10403CX, Tahe Oilfield） at different temperatures can be obtained and the depth at which the maximum asphaltene flocculation would occur in boreholes can be calculated. The crude oil PVT results showed that at 50,90 and 130 ℃, the bubble point pressure of TH 10403CX crude oil was 25.2, 26,4 and 27.0 MPa, respectively. The depth of injecting asphaltene deposition inhibitors for TH10403CX was determined to be 2,700 m.

Investigation of asphaltene deposition under dynamic flow conditions

Asphaltene deposition is one of the most seri- ous problems, which usually occurs in oil wells, petroleum production, oil processing, and transportation facilities. Deposition of heavy organic components, especially asphaltene, can lead to wellbore blockage and impacts well economics due to reduction in oil production. Therefore, it is necessary to pay more attention to finding some solution to overcome this problem. In this study, a pipe-loop apparatus for investigation of oil stability was employed to measure deposition thickness using a thermal method. The effects of many factors such as oil type, oil temperature, oil velocity, inhibitors, and solvents on asphaltene deposition were investigated. The results showed that the deposition increased with the increasing value of the colloidal insta- bility index. Besides, the deposition thickness increased with the decreasing velocity of oil, but did not change with oil temperature. In addition, n-heptane could result in more deposition; however, toluene had no effect on the deposi- tion. Branched dodecyl benzene sulfonic acid （Branched DBSA） and Linear DBSA as inhibitors decreased the rate of asphaltene deposition.

Enhancing asphaltene precipitation modeling by cubic-PR solid model using thermodynamic correlations and averaging techniques

Cubic equation-of-state solid models are one of the most widely used models to predict asphaltene precipitation behavior.Thermodynamic parameters are needed to model precipitation under different pressures and temperatures and are usually obtained through tuning with multi asphaltene onset experiments.For the purpose of enhancing the cubic Peng–Robinson solid model and reducing its dependency on asphaltene experiments,this paper tests the use of aromatics and waxes correlations to obtain these thermodynamic parameters.In addition,weighted averages between both correlations are introduced.The averaging is based on reported saturates,aromatics,resins,asphaltene(SARA)fractions,and wax content.All the methods are tested on four oil samples,with previously published data,covering precipitation and onset experiments.The proposed wax-asphaltene average showed the best match with experimental data,followed by a SARA-weighted average.This new addition enhances the model predictability and agrees with the general molecular structure of asphaltene molecules.

Study of asphaltene dispersion and removal for high-asphaltene oil wells

Many wellbores are blocked by asphaltene deposits,which lead to production problems in the oilfield development process.In this paper,methods such as elemental analysis,and solvent extraction are adopted for the study of wellbore blockages.The content of organic matter in blockages is higher than 96% and asphaltene is the main component of the organic matter with n-heptane asphaltene content of 38%.Based on the above analyses,an agent for asphaltene dispersion and removal（named as SDJ） was developed.The performance of the SDJ agent was evaluated,and it was found that the dissolution rate of asphaltene can reach 2.9 mg.mL-1.min-1 at 60 oC.SDJ agent（1wt%） was added to crude oil with a colloid instability index greater than 0.9 can effectively inhibit asphaltene deposition in the wellbore.By the viscosity method,the dissolution amount of SDJ agent was calculated,and it was found that when the viscosity of the system is around 2,000 mPa.s（the common viscosity of crude oil）,the amount of SDJ agent added to the blockage was at least 96 g per 100 g blockages.Therefore,SDJ agent has promising application for dispersion and removal of asphaltene deposition in high-asphaltene wells.

Asphaltene aggregation studied by molecular dynamics simulations:role of the molecular architecture and solvents on the supramolecular or colloidal behavior

Asphaltene aggregation is a subject under vivid discussion:There are several parameters one needs to determine before its behavior can be mastered and better target solutions can be tailored.The nature of asphaltene aggregation(colloidal or supramolecular)and the role of solvents and their mixtures are among the least understood parameters in asphaltene science.This paper addresses molecular dynamic simulations to correlate the aggregation properties of asphaltenes,their molecular structure and the concentration of these solvents.We show that the formation of the nanoaggregate depends,primarily,on the size of the conjugated core and on the eventual presence of polar groups capable of forming H-bonds.Heteroatoms on the conjugated core do not change their shape or type of aggregation but may induce stronger π-π interactions.The macroaggregation formation depends upon the length of the lateral chains of asphaltenes and also on the presence of polar groups at its end.Moreover,n-heptane and water may interact selectively with asphaltenes in function of their molecular architecture.Given this fact and the aggregation behavior observed,we advocate toward the assumption that a colloidal behavior of asphaltenes might be a particular case of a more general model,based on a supramolecular description.

Isomerization of n-pentane catalyzed by amide-AlCl3-based ionic liquid analogs with various additives

The isomerization of n-pentane to generate high-quality blending components for clean gasoline was catalyzed by several amide-AlCl3-based ionic liquid(IL) analogs with various amides as donor molecules. The catalytic performance of these IL analogs was evaluated in a magnetic agitated autoclave operated in batch mode.IL analog based n-methylacetamide(NMA)-AlCl3 with the amide/AlCl3 molar ratio of 0.65 showed excellent performance toward n-pentane isomerization because 0.65 NMA-1.0 AlCl3 had a low viscosity and bidentate coordination structure. The influences of reaction time, reaction temperature, and stirring speed on the catalytic performance were also investigated. Optimal reaction conditions comprised the reaction time of 1 h, the reaction temperature of 40 °C, and the stirring speed of 1500 r·min-1. Under optimal condition, the n-C5 conversion,research octane number(RON) increment, total liquids yield, and isoparaffin yield in isomerized oil were56.80%, 13.51, 89.90 wt%, and 44.32 wt%, respectively. A new mathematical model was constructed to predict the relationships among RON increment, RON increment/n-C5 conversion ratio, and n-C5 conversion. The new model indicated that an appropriate conversion per pass of n-C5 did not exceed 50%–55%. Various cycloparaffin additives were used to improve the catalytic performance of 0.65 NMA-1.0 AlCl3. The n-C5 conversion increased from 56.80% to 67.32%. The RON increment, total liquids yield, and isoparaffin yield reached 17.83, 97.36 wt%,and 63.74 wt%, respectively.

Investigation on hydrate growth at the oil–water interface:In the presence of asphaltene

Natural gas hydrates can readily form in deep-water oil production processes and pose a great threat to the oil industry.Moreover,the coexistence of hydrate and asphaltene can result in more severe challenges to subsea flow assurance.In order to study the effects of asphaltene on hydrate growth at the oil-water interface,a series of micro-experiments were conducted in a self-made reactor,where hydrates nucleated and grew on the surface of a water droplet immersed in asphaltene-containing oil.Based on the micro-observations,the shape and growth rate of the hydrate shell formed at the oil-water interface were mainly investigated and the effects of asphaltene on hydrate growth were analyzed.According to the experimental results,the shape of the water droplet and the interfacial area changed significantly after the formation of the hydrate shell when the asphaltene concentration was higher than a certain value.A mechanism related to the reduction of the interfacial tension caused by the absorption of asphaltenes on the interface was proposed for illustration.Moreover,the growth rate of the hydrate shell decreased significantly with the increasing asphaltene concentration under experimental conditions.The conclusions of this paper could provide preliminary insight how asphaltene affect hydrate growth at the oil-water interface.

Comparative evaluation for catalytic gasification of petroleum coke and asphaltene in subcritical and supercritical water

Subcritical and supercritical water gasification of petroleum coke and asphaltene was performed at variable temperatures(350–650°C),feed concentrations(15–30 wt%)and reaction times(15–60 min).Nickel-impregnated activated carbon(Ni/AC)was synthesized as a catalyst for enhancing syngas yields at optimal gasification conditions(650°C,15 wt%and 60 min).Structural chemistry of precursors and chars developed at different gasification temperatures was studied using physicochemical and synchrotronbased approaches such as carbon–hydrogen–nitrogen–sulfur(CHNS)analysis,thermogravimetric and differential thermogravimetric analysis(TGA/DTA),scanning electron microscopy(SEM),Fourier-Transform Infrared spectroscopy(FTIR),Raman spectroscopy,X-ray diffraction(XRD)and X-ray absorption spectroscopy(XAS).Asphaltene testified to be a better precursor for catalytic hydrothermal gasification leading to 11.97 mmol/g of total gas yield compared to petroleum coke(8.04 mmol/g).In particular,supercritical water gasification using 5 wt%Ni/AC at 650°C with 15 wt%feed concentration for 60 min resulted in 4.17 and 2.98 mmol/g of H_2from asphaltene and petroleum coke,respectively.Under the same conditions,the respective CH_4yields from catalytic gasification of asphaltene and petroleum coke were 2.54and 1.07 mmol/g.Nonetheless,asphaltene also seemed to an attractive feedstock for the production of highly aromatic chars through hydrothermal gasification.