Steady State Size Distribution of Asphaltenes by Flocculation From Toluene–n-Heptane Mixtures

Abstract

The aggregation mechanisms of asphaltenes have been the subject of several recent studies. In this work, we have studied the effect of inhibitors on size distribution of asphaltene particles, in solutions containing toluene and mixtures of n-heptane and toluene. The asphaltenes used have been extracted from Marlim crude oil, using a modified procedure IP-143/82. Several solutions containing one percent volume of asphaltenes have been prepared in pure toluene and in toluene and n-heptane mixtures with and without inhibitors and have been homogenized during a period of 24 h. The particles sizes were determined by filtering the solutions through a set of standard filters ranging from 0.45 to 0.02 µm pore size. In addition, from the saturated filtered solution of asphaltene in toluene, three other solutions were prepared having 10, 20, and 30% volume of n-heptane and were homogenized for 24 h. Again the size distribution of precipitated particles was obtained by filtering. The concentration of asphaltenes remaining in the solution was measured directly by evaporation or by spectroscopy. The results have shown that large part of asphaltenes remain as colloidal particles in the size range tested in toluene solution without inhibitor. On the solutions in which inhibitors were used, one of the inhibitors effectively prevented flocculation, concentrating the asphaltene particles on the smaller size range even on mixtures containing 20 and 30% volume of n-heptane, which is a strong flocculating agent.     

Investigation of Molecular Weight and Aggregation of Asphaltenes in Organic Solvents Using Surface Tension Measurements

Abstract

The physico-chemical behavior of asphaltene is very useful to assist prediction and control the mechanisms of asphaltene deposition during the production of petroleum fluids. It has been realized that the first step in the formation of precipitated asphaltene particles is the self-aggregation mechanism to form colloidal particles or pseudo-micelles in several solvents. In this work, the critical micelle concentration (CMC) of two asphaltene fractions extracted from vacuum residues (VR) were obtained by surface tension measurements, using aromatic solvents. The molecular weight (1094-565 g/mol), calculated from average radii of the asphaltene molecules adsorbed at the air–solvent interface, are also in agreement with the values for small aggregates reported using small angle X-ray scattering.     

Effect of pressure,temperature, and mass fraction of CO2 on the stability of the asphaltene constituents in crude oil

This paper focus on the main influence factors (temperature, pressure, and mass fraction of CO₂) on the state of asphaltene in the crude oil during CO₂ flooding by using high temperature and high pressure microanalysis system of solid precipitation. For the simulated oil sample – CO₂ system, the state of asphaltene is not affected by temperature within this range of 50°C to 100°C, the particle size of the asphaltene has an increase with the increase of the pressure from 8MPa to 40 MPa. When the mass fraction of CO₂ is less than 35%, the state of the asphaltene has not changed and the asphaltene particles are in a suspension state. When the mass fraction of CO₂ increases to 40%, the aggregation of the asphaltenes occurs and then form precipitation. With the further increase of the mass fraction of CO₂, the particle of the asphaltene aggregates has a significant increase. For the field development project design of CO₂ flooding, the influence of the temperature can be ignored, the appropriate mass fraction of CO₂ is below 35% and the gas injection pressure should maintain a relatively low value. The results can provide a theoretical basis to avoid the asphaltene precipitation during CO₂ flooding.     

Preliminary Study of the Effect of Pressure on Asphaltene Disassociation by Molecular Dynamics

Abstract

Preliminary studies of the effect of pressure on a system composed of 32 asphaltene molecules immersed in a solvent (pentane or toluene) were carried out. In this case, this system was randomly distributed into a cubic box of 49430.9 Å³ of volume. The NPT simulations showed spontaneous asphaltene disassociation when an asphaltene aggregate was immersed in toluene as a function of the pressure. Among the main configurations found, offset π-stacked geometry was the most frequently observed stacking form. Calculation of the radial distribution function on the system also revealed that the nearest asphaltene molecules have an average separation distance around 3.8 Å. This is a value in agreement with the classical model for asphaltene aggregates developed almost 40 years ago. Some possible asphaltene micelle formation and phase transitions will be described.     

胶质沥青质相互作用浅析

为认识胶质沥青质之间的相互作用,以委内瑞拉、辽河减压渣油为研究对象,测定了向沥青质-甲苯溶液中加入不同量的胶质得到的溶液的黏度、电导率以及各自的分子量。结果表明,辽河和委内瑞拉减压渣油的沥青质浓度较低时各浓度的胶质对沥青质的作用主要以分散作用为主;而沥青质浓度较高时低浓度的胶质对沥青质主要以分散作用为主,但随着胶质浓度的增大,吸附作用大于分散作用。由此推断,胶质与沥青质间存在着吸附与解缔的平衡,当平衡打破后,两者的作用会发生变化。     

The Role of Asphaltene Solubility and Chemical Composition on Asphaltene Aggregation

Abstract

Asphaltenes from four different crude oils (Arab Heavy, B6, Canadon Seco, and Hondo) were fractionated in mixtures of heptane and toluene and analyzed by small angle neutron scattering (SANS). Fractionation appeared to concentrate the most polar species into the least soluble sub-fraction as indicated by elemental analysis. SANS results indicated a wide spectrum of asphaltene aggregate sizes and molecular weights; however, the less soluble (more polar) fraction contributed the majority of the species responsible for asphaltene aggregation in solution. This more polar, less soluble fraction is likely the major cause for many petroleum production problems such as deposition and water-in-oil emulsion stabilization. A comparison of molecular weight and aggregate size indicated that asphaltenes formed fractal aggregates in solution with dimensions between 1.7 and 2.1. This was consistent with the “archipelago” model of asphaltene structure. Resins were shown to effectively solvate asphaltene aggregates as observed by an increase in asphaltene solubility, reduction in aggregate size and molecular weight, and an increase in the fractal dimension to ? 3.     

Determining the Particle Size of Asphaltenes

Abstract

Study of heavy organics and their behavior is of great importance while occurrence of their deposition in production and processing of hydrocarbon fluids. The physical properties of heavy organics, especially asphaltenes, have been a subject of controversy for several years. The aim of the present work is to determine and measure particle size of asphaltenes. Several mixtures of crude oil and n-heptane were prepared with various dilution ratios (R_v ). Two different techniques were employed to determine and measure the particle size of asphaltenes. The first was utilizing an OLYMPUS BX60, a polarizing microscope with an appropriate magnification, and the second was using high-resolution scanning electron microscopy (SEM) and X-ray diffraction techniques. The results revealed that the size of asphaltene particles is in the range of 1–4 μm for each mixture, regardless of its n-heptane content. Although the quantity of deposited asphaltene was increased by increasing the concentration of n-heptane in mixture, the particle size of asphaltene was independent of the n-heptane concentration.     

Experimental and modeling analysis of asphaltene precipitation in the near wellbore region of oil wells

In this work, effect of reservoir temperature (in a range of 50–100°С) on the amount of asphaltene precipitation was determined. Rate of asphaltene precipitation was increased by increasing temperature. Damaged permeability of carbonate core samples was investigated at different asphaltene contents conducting core flood tests. The results showed the experimental and predicted data of damaged permeability ratio due to asphaltene precipitation matched. Moreover, the optimum mass concentration of components of the developed asphaltene inhibitor was determined by measuring interfacial tension on the boundary of oil and inhibitor solution. In addition, the change in the concentration of asphaltene inhibitor was simulated depending on the radial distance to well, production time and type of isotherm.     

Metal porphyrin occlusion: Adsorption during asphaltene aggregation

Metal compounds such as vanadyl and nickel porphyrins present in crude oils are associated to the most polar fraction defined as asphaltenes. The amount and kind of these compounds in the crude oil depend of the variations in origin, maturity, pressure, and temperature. During the asphaltene colloid formation the metal porphyrins could be trapped, occluded, or adsorbed, protecting these compounds from oxidation or chemical degradation. In this work the authors induce the aggregation of asphaltenes by changing the solubility parameter of the media in presence of metal porphyrins. UV-vis absorbance is used to monitored asphaltene aggregation at 350 nm to follow the variations in asphaltene aggregation and 405 nm to follow the porphyrin Soret band. The results showed that more than 50% of the porphyrins were trapped inside the asphaltene aggregate and posterior re-dissolution of the aggregates in toluene showed very low release of the porphyrins, demonstrating the strong interaction between the porphyrin and asphaltenes during the aggregation.     

双亲分子头部官能团对石油沥青质胶团分散性的影响

 为理解双亲分子对甲苯溶液中石油沥青质胶团形状、溶剂化程度以及颗粒间相互作用的影响,测定了其甲苯溶液的黏度,采用Pals-Rhodes方程、Eiler方程、Kuhn-Kuhn方程和Leighton-Acrivos方程等经验方程关联了黏度与体积分数之间的关系。由Pals-Rhodes方程得到的形状参数α和溶剂化参数K表明沥青质胶团为球形,添加双亲分子后其溶剂化程度增加,但其形状仍为球形。由Eiler方程分析表明,添加双亲分子后,其最大堆积体积分数φm增加,说明沥青质胶团的分散度增加。Kuhn-Kuhn所计算出的形状因子严重偏离球形,因未考虑溶剂化效应和颗粒间的相互作用,故其结果与Pals-Rhodes方程得到的结果差别较大。由Leighton-Acrivos方程得到的相互作用系数表明,添加双亲分子后,沥青质胶团之间的相互作用程度增加。     

MOLECULAR MECHANICS OF AGGREGATES OF ASPHALTENES AND RESINS OF THE ATHABASCA OIL

An analysis of the effects of an almost continuous chemical distribution of asphaltenes and resins on the molecular recognition processes occurring in crude oil indicates that their aggregates will have a broad distribution both in the chemical composition and in the strength of the intermolecular interactions responsible for the aggregation. Then, crude oil cannot be described just as a sol formed by solid asphaltene particles dispersed by resins or as a simple micellar system of asphaltene and resin molecules. The molecular aggregates may vary from solid particles formed by asphaltenes and resins to loosely bound micelles with quite short lifetimes. These different aggregates may coexist within the crude oil and many will exchange components with others. The entropic contributions to the changes in free energy upon aggregation were also discussed. Molecular mechanics calculations showed that a model asphaltene aggregate from Athabasca exhibits stronger interactions with its resins than with solvents such as toluene and n-octane. The resins showed a considerable selectivity for the different adsorption sites of the asphaltene aggregate. This selectivity was stronger than that found for the solvent molecules, indicating that it is enthalpically more favorable for them to form aggregates with the asphaltenes. The selectivity may also help to explain the specificity of some resins that are able to disperse only the asphaltenes of certain types of crude oils while failing to do the same for others.     

Application of Coker Gas Oil Used as Industrial Hydrogen Donors in Visbreaking

Effectiveness of coker gas oil (CGO) used as industrial hydrogen donors in the visbreaking was revealed. Hydrogen-transferring abilities of different CGO narrow fractions were first analyzed. The fraction of 350–420°C (HDII) turned out to be the best selection as hydrogen donors and then we did visbreaking experimental tests. The results show that, in contrast with conventional visbreaking, the addition of HDII achieves higher conversion of residues to desirable liquid product and effectively suppresses coke formation: the coke induction period is prolonged from 17 to 27 min and the liquid-coke particle size decreases from 0.307 to 0.186 μm. The hydrogen shuttle between asphaltene and hydrogen donors is of great significance during this thermal processing.     

CHARACTERIZATION OF ASPHALTENE PARTICLES BY LIGHT SCATTERING AND ELECTROPHORESIS

The solubility of asphaltenes in heptane/toluene mixtures was studied at several temperatures. A significant increment in asphaltene solubility was observed when the temperature increases from 0°C to 20°C and a moderate increase when the temperature rose from 20°C to 50°C. These results indicate that asphaltenes behave as a higher consulate temperature system, similar to nonpolar waxes. Examined by photon correlation spectroscopy, diameters from the particles formed a range between 125 and 400 nm, depending on the amount of non-solvent (n-heptane) used for the precipitation process and the initial concentration of asphaltenes. The particles presented a small positive surface potential that was not altered by the addition of resins.     

Synthesis and Characterization of Ultrafine TATB

An acid recrystallization process for synthesis of ultrafine TATB (UF-TATB) of median particle size < 5 µm is described. The process uses production grade TATB (PG-TATB) of median particle size > 50 µm. PG-TATB is made soluble in DMSO-alkali. Acidification of this basic solution is done with dilute aqueous nitric acid, which causes precipitation of UF-TATB through a reaction crystallization process. The process is simple, economical, and easy to scale up. The effect of various process parameters such as acid concentration and neutralization time on particle size is studied and discussed. UF-TATB is characterized for purity, chloride content, particle size, DSC, STA, SEM, sensitivity, etc., and results have been compared with PG-TATB. Along with particle size, the chloride impurity in UF-TATB is also reduced from 0.7 to < 0.13%. SEM analysis reveals regular bi-pyramidal shape with sharp edges and corners of UF-TATB crystals compared to porous and rough surfaces of PG-TATB crystals. There is an impact sensitivity gain in UF-TATB. This may be due to the ultrafine nature of the particles.     

Composition Choice and Formulation of Three HMX-Based Research Explosives

The composition and formulation for three research explosives having similarities to military explosives are described. The primary energetic ingredient in each is cyclotetramethylene-tetranitramine (HMX), whose particle size is limited to a range of 125–210 μm to reduce variations in shock reactivity and performance. The binder in each explosive is hydroxy-terminated polybutadiene (HTPB). The first composition contains only these two components. Aluminum with a nominal particle size of 5 μm is incorporated into the second composition. The third composition contains ammonium perchlorate (AP) with a nominal particle size of 200 μm in addition to the aluminum. The explosives are designed with features to allow for comparisons in shock reactivity and performance and to elucidate the roles of HMX, Al, and AP.     

双亲分子头部官能团对石油沥青质胶团分散性的影响Ⅱ.石油沥青质胶团形状、溶剂化程度与相互作用

为理解双亲分子对石油沥青质甲苯溶液巾沥青质胶团形状、溶剂化程度以及颗粒间相互作用的影响,测定了其甲苯溶液的黏度,采用Pals-Rhodes方程、Eiler方程、Kuhn-Kuhn方程和Leighton-Acrivos方程关联了黏度与体积分数之间的关系.由Pals-Rhodes方程得到的形状参数α和溶剂化参数K表明.在沥青质甲苯溶液中沥青质胶用为球形.添加双亲分子后其溶剂化程度增加,但其形状仍为球形.由Eiler方程分析表明,沥青质甲苯溶液添加双亲分子后,沥青质最大堆积体积分数ψ_m增加,说明沥青质胶团的分散度增加.由Kuhn-Kuhn方程计算所得沥青质甲苯溶液中沥青质颗粒的形状因子严重偏离球形,因未考虑溶剂化效应和颗粒间的相互作用,故与Pals-Rhodes方程得到的结果差别较大.由Leighton-Acrivos方程得到的相互作用系数表明,沥青质甲苯溶液添加双亲分子后,沥青质胶团之间的相互作用程度增加.     

Assembly of asphaltene molecular aggregates as studied by near-UV/visible spectroscopy: II. Concentration dependencies of absorptivities

The properties of molecular aggregation in toluene solutions of a crude oil and solid asphaltenes are determined almost solely by the concentration of asphaltenes, as shown by absorptivity measurements at 315–750 nm. From non-monotonic concentration dependencies of absorptivities, it is concluded that asphaltene monomers are abundant in solutions with asphaltene concentrations below 1–5 mg/l, while molecular aggregates are effectively formed above 20–25 mg/l. The most stable oligomers are a dimer and a dimer pair (Yen's “nanocrystallite” [NC]). Nanocrystallites act as building blocks for more complex aggregates at asphaltene concentrations exceeding 90–100 mg/l. These optical absorption results are supported by studies of Rayleigh scattering in asphaltene solutions.     

双亲分子头部官能团对石油沥青质胶团分散性的影响

为认识含有不同头部官能团的双亲分子对沥青质胶团分散性的影响,测定了添加十二烷基苯磺酸(DBSA) 、十二烷基苯酚(DP)和十二醇的沥青质甲苯溶液的黏度变化规律,通过线性拟合得到其特性粘度,进而计算得到无限稀释情况下沥青质胶团直径。对比添加双亲分子前后,比浓黏度随浓度的增加速度和胶团直径的变化都表明：双亲分子头部官能团酸性越强,其与沥青质的作用越强,在沥青质表面吸附的越多。酸性较强的十二烷基苯磺酸在沥青质表面能形成多层吸附或者发生聚集,十二烷基苯酚只能形成单层吸附,而十二醇则对沥青质溶液的黏度几乎没有影响,可能没有发生吸附。     

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.     

The Role of Asphaltene Solubility and Chemical Composition on Asphaltene Aggregation

Asphaltenes from four different crude oils (Arab Heavy, B6, Canadon Seco, and Hondo) were fractionated in mixtures of heptane and toluene and analyzed by small angle neutron scattering (SANS). Fractionation appeared to concentrate the most polar species into the least soluble sub-fraction as indicated by elemental analysis. SANS results indicated a wide spectrum of asphaltene aggregate sizes and molecular weights; however, the less soluble (more polar) fraction contributed the majority of the species responsible for asphaltene aggregation in solution. This more polar, less soluble fraction is likely the major cause for many petroleum production problems such as deposition and water-in-oil emulsion stabilization. A comparison of molecular weight and aggregate size indicated that asphaltenes formed fractal aggregates in solution with dimensions between 1.7 and 2.1. This was consistent with the “archipelago” model of asphaltene structure. Resins were shown to effectively solvate asphaltene aggregates as observed by an increase in asphaltene solubility, reduction in aggregate size and molecular weight, and an increase in the fractal dimension to ~ 3.