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.     

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.     

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.     

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.     

DPD Molecular Simulations of Asphaltene Adsorption on Hydrophilic Substrates: Effects of Polar Groups and Solubility

Adsorption of asphaltenes onto a polar substrate (e.g., a mineral) was modeled with dissipative particle dynamics (DPD) simulations, using continental asphaltene models. The adsorption mechanisms in 10–20% wt, of asphaltene in toluene/ heptane solutions were studied (well above the solubility limit). The structure in the adsorbed layer was highly sensitive to the presence of polar groups in the alkyl side chains and heteroatom content in the aromatic ring structure. Four types of asphaltene models were used: completely apolar (zero adsorption), apolar chains and polar heteroatoms, polar chains and no heteroatoms, and polar chains and heteroatoms (maximum adsorption). One hundred asphaltene monomers were distributed homogeneously in the solvent initially, in a ～(10 nm)³ domain.

Asphaltene monomers adsorbed irreversibly on the substrate via the polar group in the side chains, resulting in an average perpendicular orientation of the aromatic rings relative to the substrate. More frequent π–π stacking of the aromatic rings occurred for less solubility (more heptane), as in aggregates. With apolar side chains, only the heteroatoms in the aromatic ring structure had affinity to the substrate, but the ring plane did not have any preferred direction.

An important finding is that the aromatic ring assemblies “shielded” the substrate and polar groups that were anchored to the substrate, resulting in an effective non-polar surface layer seen by asphaltenes in the bulk, leading to much lower adsorption probability of the remaining asphaltenes. This “adsorption termination” effect leads to mono-layer formation. Continued adsorption with multilayering and reversible nanoaggregate adsorption occurred when both side chains in the model asphaltene (located on opposite sides of the aromatic sheet) contained polar groups, with a higher probability of exposing further polar groups to the bulk asphaltene. The general conclusion is that the number and position of the polar groups in side chains determine to a large degree the adsorption and aggregation behavior/efficiency of (continental) asphaltenes, in line with experimental evidence. The heteroatoms in the aromatic ring structure plays a more passive role in this context, only by providing organization via more π–π stacking in the adsorbed layer, and in aggregates.     

TiO2纳米酶絮凝动力学

以聚丙烯酰胺(PAM)为絮凝剂,纳米TiO2为固定化酶载体材料,木瓜蛋白酶为酶模型制备纳米絮凝酶.结合粒度分析、SEM、EDS等表征手段,考察PAM种类、加量及体系pH对高分子凝胶絮凝与沉降动力学的影响.结果表明通过氢键、静电吸附和架桥等作用,纳米酶和PAM间产生有效的絮凝.TiO2纳米酶的絮凝沉降速度、体系浊度、絮团大小和紧实程度随PAM用量不同而改变.适量的PAM产生高沉降速度,低浊度,稳定、大絮团的强絮凝,其中nPAM絮凝酶的沉降速度最快,絮团最大.过量的絮凝剂导致絮团脱稳.调控体系酸碱度亦可有效调控PAM絮凝动力学行为.比较nPAM和cPAM,发现nPAM絮凝体对pH有较高稳定性,cPAM絮凝体受pH影响显著.故可以根据酶结构与特性,调节絮凝剂加量和体系酸碱度设计出微纳尺度可调的固定化酶.     

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.      

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.     

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.     

Kinetics of crude oil combustion

In this research, thermal characterization and kinetics of Karakus crude oil in the presence of limestone matrix is investigated. Thermogravimetry (TG/DTG) is used to characterize the crude oil in the temperature range of 20-900°C, at 10°C min ^-1 heating rate using air flow rate of 20 mL min ^-1. In combustion with air, three distinct reaction regions were identified known as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO). Five different kinetic methods used to analyze the TG/DTG data to identify reaction parameters as activation energy and Arrhenius constant. On the other hand different f(α) models from literature were also applied to make comparison. It was observed that high temperature oxidation temperature (HTO) activation energy of Karakus crude oil is varied between 54.1 and 86.1 kJ mol ^-1, while low temperature oxidation temperature (LTO) is varied between 6.9 and 8.9 kJ mol ^-1.     

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.     

Calculation of Dipole Moment of Fractal Asphaltene Cluster

Computer simulation has been used to investigate the cluster formation of the asphaltenes. Asphaltene nanoaggregates, forming a cluster, possessed permanent dipole moments. The influence of various factors, namely, temperature of the medium, size and dipole moment of the nanoaggregates, on the dipole moment of the asphaltene cluster was studied. The orientation interactions between the nanoaggregates were demonstrated to rise with increasing specific dipole moment of the nanoaggregates. It is has been found that the dipole moment of the asphaltene cluster varies according to power law in relation to the number of the nanoaggregates, forming the cluster.     

Pyrolysis Analysis and Kinetics of Crude Oils

This research presents the results of an experimental study on the determination of pyrolysis behaviour and kinetics of six crude oils by differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). Crude oil pyrolysis indicated two main temperature ranges where loss of mass was observed. The first region between ambient to 400°C was distillation. The second region between 400 and 600°C was visbreaking and thermal cracking. Arrhenius-type kinetic model is used to determine the kinetic parameters of crude oils studied. It was observed that as crude oils gets heavier (°API decreases) cracking activation energy increases. Activation energy of cracking also show a general trend with asphaltene content. This revised version was published online in July 2006 with corrections to the Cover Date.     

Asphaltene precipitation modeling through ACE reaping of scaling equations

Precipitation and deposition of asphaltene have undesirable effects on the petroleum industry by increasing operational costs due to reduction of well productivity as well as catalyst poisoning.Herein we propose a reliable model for quantitative estimation of asphaltene precipitation.Scaling equation is the most powerful and popular model for accurate prediction of asphaltene precipitated out of solution in crudes without regard to complex nature of asphaltene.We employed a new mathematical-based approach known as alternating conditional expectation(ACE)technique for combining results of different scaling models in order to increase the accuracy of final estimation.Outputs of three well-known scaling equations,including Rassamdana(RE),Hu(HU),and Ashoori(AS),are input to ACE and the final output is produced through a nonlinear combination of scaling equations.The proposed methodology is capable of significantly increasing the precision of final estimation via a divide-andconquer principle in which ACE functions as the combiner.Results indicate the superiority of the proposed method compared with other individual scaling equation models.     

Experimental Investigation of Asphaltenes Flocculation Threshold in Crude Oils Using Different Methods: Comparative Study

Despite some recent progress trustworthy methods to predict the flocculation onset in crude oils are still needed. In this article, different experimental methods, like the density measurement method, the optical and the spot techniques based on the mixture of crude oil + toluene or cyclohexane + n-heptane, respectively, are applied to assess changes of aggregation occurring in crude oil under influence of physical and chemical factors as well as under variable temperature conditions. The solubility parameters of Hildebrand have also been used to predict the flocculation threshold. It turned out that the findings achieved by the spot method and the optical technique are in excellent agreement with break points of the reduced density curves obtained by the density measurement method for crude oils of different geographical origins. Using the solubility parameters of Hildebrand leads to comparable results. All these achievements confirm the density measurement method as a new possibility for reliably determining the flocculation onset in crude oils systems. With respect to temperature effects, changes of the oil microstructure could be detected as function of the temperature by means of the differential scanning calorimetry. In particular the thermal curves behavior of certain crude oils confirmed the existence of aggregation processes.      

Computer Simulation of Bridging Flocculation Processes: The Role of Colloid to Polymer Concentration Ratio on Aggregation Kinetics

The flocculation of colloidal particles by adsorbing polymers is one of the central issues of colloid science and a very important topic in many industrial, biological, and environmental processes. We report a computer simulation study of a 2- and 3-dimensional model for bridging flocculation betweenlarge linear polymer chains and comparatively small colloidal particles,where the structure and growth kinetics of cluster formation are investigated. This model was developed within the framework of the cluster–cluster aggregation model using mass and fractal dimension dependent diffusion constants, where bridging flocculation is seen as a case of heterocoagulation in which, in addition, macromolecule configurations and lengths play an important role. The simulation of aggregate structure and formation kinetics obtained at different (i) relative particle concentrations, (ii) polymer chain conformations, and (iii) sticking probabilities are described from a qualitatively and quantitative point of view. The results suggest that the formation of large aggregates is a slow process, controlled by the reactivity of the clusters, even when the reaction between microcolloids and macrochains is very fast. Aggregation kinetics are strongly dependent on the particle/chain concentration ratio and on the configurational properties of the chains. It is shown that the scaling laws which are valid for homocoagulation processes are also applicable to the kinetics of bridging flocculation. The corresponding scaling exponents have been calculated.     

测定心血管紧张素转化酶抑制剂体外抑制动力学的反相HPLC法

报道一种用反相ＨＰＬＣ技术简便、有效地研究心血管紧张素转化酶抑制剂体外抑制动力学的新方法。该法利用马尿酰－甘氨酰－甘氨酸作酶底物，反相ＨＰＬＣ跟踪监测酶解产物马尿酸的浓度随时间变化来研究酶解反应的历程     

Removal of Tannic Acid by Chitosan and N-Hydroxypropyl Trimethyl Ammonium Chloride Chitosan: Flocculation Mechanism and Performance

The cationic organic flocculant chitosan and its derivative, N-hydroxypropyl trimethyl ammonium chloride chitosan (HTCC), were used in the flocculation of tannic acid, the impurity widespread in Chinese medicine water extractions. This study aimed at investigating the flocculation performance and mechanism of chitosan and HTCC on the tannic acid colloidal particles. The results showed that chitosan and HTCC effectively flocculated the tannic acid solution and the mechanism was mainly for the adsorption bridging and charge neutralization by hydrogen bonding, electrostatic interaction, and hydrophobic interaction. Meanwhile, the charge neutralization of HTCC was stronger than that of chitosan. The optimal flocculation conditions of chitosan and HTCC on tannic acid were achieved.     

Light crude oil combustion in the presence of limestone matrix

In this study the combustion characteristics of crude oils (Karakuę and Beykan) in the presence of a limestone matrix were determined using the thermogravimetry (TG/DTG). Experiments were performed at a heating rate of 10°C min^-1, whereas the air flow rate was kept constant at 10 L h^-1 in the temperature range of 20-900°C. In combustion with air, three distinct reaction regions were identified in all crude oil/limestone mixtures studied known as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO). The individual activation energies for each reaction region may be attributed to different reaction mechanisms, but they do not give any indication of the contribution of each region to the overall reactivity of the crude oils. Depending on the characteristics, the mean activation energy of samples varied between 50.3 and 55.8 kJ mol^-1. This revised version was published online in August 2006 with corrections to the Cover Date.     

Kinetics Model of Destabilization of Oil Droplets in Oily Wastewater Emulsions

In this article, a mathematical model that accounts for the kinetics of flocculation and coalescence of emulsion drops was developed to quantify the kinetics of emulsion stability. The model is similar to that developed by Borwankar et al. in 1992 with corrections in coalescence rate constant and collision efficiency factor. It includes a term to describe efficiency of collisions. Also, the coalescence rate constant was defined as a function of the total number of particles that were present in the system at the moment. The model has four adjustable parameters, and nonlinear least square optimization is used to obtain the adjustable parameters. The obtained adjustable parameters by the model served as parameters that can be used to quantitatively evaluate the effectiveness of a set of different demulsifiers by measuring total numbers of drops versus time and by determining the adjustable parameters and comparing them. The results of the presented model and the model of Borwankar et al. were compared with experimental data. The results of the new model were in good agreement with experimental data and showed the model's ability for dispalying the behavior of droplets during the destabilization processes of emulsions.