A further investigation to mechanism of the electrorheological effect of waxy oils:Behaviors of charged particles under electric field

Exposing waxy oils to an electric field may significantly improve their cold flowability.Our previous study has shown that interfacial polarization,i.e.,charged particle accumulation on the wax particle surface,is the primary mechanism of the electrorheological behavior of waxy oils.However,the way that charged particles interact with wax particles under an electric field remains unknown.In this study,we found no viscosity and impedance change for two waxy crude oils after their exposure to a high-voltage electric field.However,the yield stresses were reduced obviously.We thus proposed that the collision of colloidal particles such as resins and asphaltenes with the wax particles could be an essential mechanism that the wax particle structure was weakened.To verify this hypothesis,a series of ad hoc experiments were carried out,i.e.,by performing electrorheological tests on model waxy oils containing additives removable under an electric field,including electrically-neutral colloidal particles(Fe3O4),charged colloidal particles(resins),and oil-soluble electrolyte(C22H14CoO4),respectively,and demonstrated that upon application of a high-voltage electric field,charged particles in a waxy oil may move and thus collide with wax particles,and consequently adhere to the wax particle surface.The particle collision results in damage to the wax particle network,and the electrostatic repulsion arising from the adhesion of the charged particle on the wax particle diminishes attraction between wax particles.This study clarifies the process of interfacial polarization.

Prediction Model of Wax Deposition Rate in Waxy Crude Oil Pipelines by Elman Neural Network Based on Improved Reptile Search Algorithm

A hard problem that hinders the movement of waxy crude oil is wax deposition in oil pipelines.To ensure the safe operation of crude oil pipelines,an accurate model must be developed to predict the rate of wax deposition in crude oil pipelines.Aiming at the shortcomings of the ENN prediction model,which easily falls into the local minimum value and weak generalization ability in the implementation process,an optimized ENN prediction model based on the IRSA is proposed.The validity of the new model was confirmed by the accurate prediction of two sets of experimental data on wax deposition in crude oil pipelines.The two groups of crude oil wax deposition rate case prediction results showed that the average absolute percentage errors of IRSA-ENN prediction models is 0.5476% and 0.7831%,respectively.Additionally,it shows a higher prediction accuracy compared to the ENN prediction model.In fact,the new model established by using the IRSA to optimize ENN can optimize the initial weights and thresholds in the prediction process,which can overcome the shortcomings of the ENN prediction model,such as weak generalization ability and tendency to fall into the local minimum value,so that it has the advantages of strong implementation and high prediction accuracy.

Rheo-optic in situ synchronous study on the gelation behaviour and mechanism of waxy crude oil emulsions

An improved rheo-optic in situ synchronous measurement system was employed to investigate the gelation behaviour and mechanism of waxy crude oil emulsions. By combining transmitted natural light and reflected polarized light microscopy, a multiangle composite light source was built to achieve the simultaneous observation of wax crystals and emulsified water droplets, as well as their dynamic aggregation process. Main outcomes on the microscopic mechanism were obtained by developed microscopic image processing method. It was found that the microstructure of W/O waxy crude oil emulsion has the evolution of “individual structure--homogeneous aggregate structure--heterogeneous coaggregate structure--floc structure” during the static cooling, which results in the four stages during gelation process. Different from previous studies, the aggregation of emulsified water droplets was found to be more significant and contributes to the formation and development of the wax crystals-emulsified water droplets coaggregate, which plays a decisive role in the further evolution of the gelled microstructure. Time series microscopic images show the dynamic aggregation of emulsified water droplets and wax crystals. Two different aggregation behaviours between wax crystals and water droplets were observed. That wax crystals can not only embed in gaps between adjacent water droplets and enhance the structure, but also surround the outside of the water droplets and continue to grow resulting in the interconnection of different coaggregates to form a larger floc structure. In addition, correlation between viscoelasticity and microstructure evolution of waxy crude oil emulsions of different water contents was discussed. With increasing water contents, the microstructure is changed from wax crystal flocculation structure as the main skeleton and the emulsified water droplets embedded in it, into the aggregation of emulsified water droplets occupying the main position. When the number of wax crystals and water droplets reaches a certain ratio, did wax crystals form coaggregates with emulsified water droplets, and the remaining wax crystals formed an overall flocculation structure, the viscoelasticity of the waxy crude oil emulsion is the highest.

Effect of nanocomposite pour point depressant EVAL/CNT on flow properties of waxy crude oil

The nanocomposite EVAL-CNT was produced by chemical grafting in the solution system through the esterification of ethylene-vinyl alcohol copolymer (EVAL) and carboxylated multi-walled carbon nanotubes (O-MWCNT), and its structural properties were characterized. The improvement of the rheological properties of the waxy oil system by the novel pour point depressant was investigated using macroscopic rheological measurements and microscopic observations. The results showed that EVAL-CNT nanocomposite pour point depressant (PPD) could significantly reduce the pour point and improve the low temperature fluidity of crude oil and had better performance than EVAL-GO at the same addition level. The best effect was achieved at the dosing concentration of 400 ppm, which reduced the pour point by 13 ℃ and the low-temperature viscosity by 85.4%. The nanocomposites dispersed in the oil phase influenced the precipitation and crystallization of wax molecules through heterogeneous crystallization templates, which led to the increase of wax crystal size and compact structure and changed the wax crystal morphology, which had a better effect on the rheological properties of waxy oil.

STUDY ON OPTIMIZATION OF DESIGN PROPOSALFOR HOT WAXY ORUDE OIL TRANSMISSIONPIPELINE AND ITS APPLICATION

A mathematical model for optlmization design of the hot waxy crude oil transmission IZipelineis studied. The dimension-reducing method is selected to solve problems raised from multivariable,restricted and non-linear planning. And the optimization design model is applied to the practical design ofHejian Shijiazhuang oil transmission pipeline. outstanding economic and social benefits have beengained.

Study on the thixotropy and structural recovery characteristics of waxy crude oil emulsion

Waxy crude oil emulsion has thixotropic properties at the temperature near gel point,which is a macromechanical characterization of the structure failure and recovery of waxy crude oil emulsion.In this paper,the thixotropic behaviors of waxy crude oil emulsion near gel point were studied using hysteresis loop formed by stress linear increase and decrease,as well as the structural recovery characteristics.The influence of the loading conditions and water content on the thixotropy of waxy crude oil emulsion were analyzed with hysteresis loop area.The concept of"structural recovery"was introduced to study the degree of structural recovery after different stewing,and influencing factors were taken into account.Results have shown that for waxy crude oil emulsion,the failure to fully restore of the structure after lysis is the cause of the formation of hysteresis loop,and the loading conditions will not affect the strength of thixotropy and the degree of structural recovery.Additionally,the dispersed phase droplets weaken the thixotropy and structure recovery characteristics of waxy crude oil emulsion,and the greater the water content,the weaker the thixotropy.The findings can help to better understand the safe and economic operation of waxy crude oil-water pipeline transportation.

Synergistic effect of magnetic field and nanocomposite pour point depressant on the yield stress of waxy model oil

Yield stress,as the key parameter to characterize the network strength of waxy oil,is important to the petroleum pipeline safety.Reducing the yield stress of waxy oil is of great significance for flow assurance.In this study,the effect of alternating magnetic field(intensity,frequency)on the yield stress of a waxy model oil with nanocomposite pour point depressant(NPPD)is systematically investigated.An optimum magnetic field intensity and frequency is found for the reduction in yield stress.When adding with NPPD,the heterogeneous nucleation of NPPD contributes to the reduction in yield stress for waxy model oil.Interestingly,the magnetic field is helpful for the modification of yield stress at a lower frequency and intensity before the optimal value;however,the modification is found to be weakened when the magnetic field is further increased after the optimal value.Possible explanation is proposed that the aggregation morphology of wax crystal would be altered and results in the release of wrapped oil phase from the network structure under the magnetic field.

Pre-heating temperature induced flowability and wax deposition characteristics of crude oil adding wax inhibitors

This paper investigated the effects of pre-heating treatment temperatures(T_(pre))on the flowability and wax deposition characteristics of a typical waxy crude oil after adding wax inhibitors.It is found that there is little difference in wax precipitation exothermic characteristics of crude oils at different T_(pre),as well as the wax crystal solubility coefficient in the temperature range of 25-30℃.For the undoped crude oil,the flowability after wax precipitation gets much improved and the wax deposition is alleviated as T_(pre)increasing.At T_(pre)=50℃,the viscosity and wax deposition rate of crude oil adding wax inhibitors are higher than those of the undoped crude oil.When the T_(pre)increases to 60,70,and 80℃,the flowability of the doped crude oil are largely improved and the wax deposition is suppressed with the T_(pre)increase,but the wax content of wax deposit increases gradually.It is speculated that,on the one hand,the T_(pre)increase helps the dispersion of asphaltenes into smaller sizes,which facilitates the co-crystallization with paraffin waxes and generates more aggregated wax crystal flocs.This weakens the low-temperature gel structure and increases the solid concentration required for the crosslink to form the wax deposit.On the other hand,the decrease in viscosity increases the diffusion rate of wax molecules and accelerates the aging of wax deposits.The experimental results have important guiding significance for the pipeline transportation of doped crude oils.

Study on the effect of CH_(4) dissolution on the microstructure of wax crystal in waxy crude oil

In this work, the influence of the dissolution of methane(CH_(4)) gas on the wax crystal of waxy crude oil and the effect on the rheology of crude oil by dissolved CH_(4) were studied comprehensively. A self-deign high-pressure micro visualization device was developed to analyze wax crystals before and after gas dissolution. The crude oil from Shengli and Nanyang was tested by the device under various gas pressures. Results showed that the viscosity, maximum shear stress and equilibrium shear stress of Shengli crude oil decreased with the increasing pressure of the dissolved CH_(4). Due to the supersaturation of dissolved gas, the viscosity, maximum shear stress and equilibrium shear stress of Nanyang crude oil decreased initially and increased with the increasing pressure of dissolved CH_(4). The change in rheology of the dissolved gas crude oil can be a combined influence of gas pressure and dissolution mechanisms caused by CH_(4). Additionally, the wax precipitation point of Shengli crude oil decreased at the saturated dissolution of CH_(4), while Nanyang crude oil showed an increasing wax precipitation temperature.Notably, the wax precipitation area, number of wax particles, and average diameter of wax crystal in both crude oils gradually decreased with dissolution. However, a saturation of CH_(4) caused a small amount of precipitation of wax crystals in Nanyang crude oil, and the small wax crystals were aggregated to form the large wax crystals. The dissolution of CH_(4) gas can affect the wax crystallization process, crystallization ability, and morphology of wax crystals that resulted in significant variation in the rheology of crude oil.

Thermodynamic Modeling of Wax Precipitation in Crude Oils

Most of the crude oils contain waxes which precipitate when temperature drops, resulting in deposition in pipelines and production equipment. It is necessary to set up a model which can predict the wax appearance tem-perature and the amount of solid precipitated in the different conditions. A modified thermodynamic solid-liquid equilibrium model to calculate wax precipitation in crude oil systems has been developed recently. The assumption that precipitated waxes consist of several solid phases is adopted in this research, and the solid-solid transition is also considered in the modified model. The properties of the pseudo-components are determined by using empirical correlations. New correlations for properties of solid-solid and solid-liquid transitions are also established in this work on the basis of the data from the literature. The results predicted by the proposed model for three crude oil systems are compared with the experimental data and the calculated results from the literature, and good agreement is observed.

A nonlinear creep damage model for gelled waxy crude

Yielding behaviors of waxy crude oil is one of the key issues of flow assurance challenges. The yielding of waxy crude under constant stress is actually a creep process of strain accumulation to structural failure,to describe the process completely and accurately is the basis of numerical simulation of restart process of the pipeline. The creep and yield behaviors of two gelled waxy crudes were investigated experimentally under different constant applied stresses. The results clearly show that the creep process of waxy crude is related to the applied stress and time. The greater the applied stress, and the longer the loaded time, the more obvious the nonlinear features. Based on the fractional calculus theory, a fractional viscous element was developed to describe the decelerated and steady creep process of gelled waxy crude. On the basis of the damage theory, an elastic damage element was proposed to describe the accelerated creep after the yielding. According to the idea of mechanical analogy, a nonlinear creep model was established by a fractional viscous element, an elastic damaged element, and an elastic element in series, which can accurately describe the whole creep and yielding process of gelled waxy crude.

Formation mechanism of condensates, waxy and heavy oils in the southern margin of Junggar Basin, NW China

It is a challenge to determine the source and genetic relationship of condensate, waxy and heavy oils in one given complicated petroliferous area, where developed multiple sets of source rocks with different maturity and various chemical features.The central part of southern margin of Junggar Basin, NW China is such an example where there are condensates, light oils, normal density oils, heavy crude oils and natural gases. The formation mechanism of condensates has been seriously debated for long time;however, no study has integrated it with genetic types of waxy and heavy oils. Taking the central part of southern margin of Junggar Basin as a case, this study employs geological and geochemical methods to determine the formation mechanism of condensates,waxy and heavy oils in a complicated petroliferous area, and reveals the causes and geochemical processes of the co-occurrence of different types of crude oils in this region. Based on detailed geochemical analyses of more than 40 normal crude oils, light oils,condensates and heavy oils, it is found that the condensates are dominated by low carbon number n-alkanes and enriched in light naphthenics and aromatic hydrocarbons. Heptane values of these condensates range from 19% to 21%, isoheptane values from1.9 to 2.1, and toluene/n-heptane ratios from 1.5 to 2.0. The distribution of n-alkanes in the condensates presents a mirror image with high density waxy crude oils and heavy oils. Combined with the oil and gas-source correlations of the crude oils, condensates and natural gas, it is found that the condensates are product of evaporative fractionation and/or phase-controlled fractionation of reservoir crude oils which were derived from mature Cretaceous lacustrine source rocks in the relatively early stage. The waxy oils are the intermediate products of evaporative fractionation and/or phase-controlled fractionation of reservoir crude oils, while the heavy oils are in-situ residuals. Therefore, evaporative fractionation and/or phase-controlled fractionation would account for the formation of the condensate, light oil, waxy oil and heavy oil in the central part of southern margin of Junggar Basin, resulting in a great change of the content in terms of light alkanes, naphthenics and aromatics in condensates, followed by great uncertainties of toluene/n-heptane ratios due to migration and re-accumulation. The results suggest that the origin of the condensate cannot be simply concluded by its ratios of toluene/n-heptane and n-heptane/methylcyclohexane on the Thompson's cross-plot, it should be comprehensively determined by the aspects of geological background, thermal history of source rocks and petroleum generation,physical and chemical features of various crude oils and natural gas, vertical and lateral distribution of various crude oils in the study area.

Performance improvement of Ethylene-Vinyl Acetate Copolymer Pour Point Depressant(EVA PPD)by adding small dosages of Laurylamine(LA)

Lauramine is widely considered to be an asphaltene flocculant,but its effect on the modification of crude oil by PPDs has been little studied.In this paper,the effect of LA dosage on the rheology improvement of EVA PPDs(100 ppm)on Qinghai waxy crude oil was investigated through rheological measurement,wax precipitating analysis,granularity test and resins/asphaltenes FTIR analysis.Compared with pure EVA,the compounding of LA and EVA obviously enhances the agglomeration degree and reduces the number of fine wax crystals,thus further enhancing the rheology of the oil samples,and the best performance is at the LA dosage of 200 ppm.At relatively small LA dosages,the LA facilitates the adsorption of EVA molecules on the asphaltene surfaces,which favors the becoming of EVA/asphaltenes composite particles;but at relatively high LA dosages,the LA makes the asphaltenes more aggregated and disturbs the EVA adsorption on the asphaltenes,which is adverse for the formation of EVA/asphaltenes compound particles.The compound particles can serve as wax precipitating templates and significantly influence its morphology,thus further improving the crude oil rheology.In consequence,the rheology improvement of EVA PPDs on Qinghai waxy crude oil first increases and then decreases with increasing the LA dosage.

Study of linseed oil,its biodiesel and xylene as flow improver for Nigerian waxy crude oils

In this study,the physicochemical properties of linseed and linseed biofuel were studied and their effect on the flow properties of Nigerian waxy crude oil at different volume fractions was investigated.The Nigerian wax crude oil was characterized for its specific gravity,API gravity,wax content,pour point and cloud point.The properties of the linseed oil and linseed biodiesel investigated include:density,specific gravity,viscosity,pour point,cloud point and flash point.Upon esterification of the free fatty acid(FFA)contained in the linseed oil reduced from 3.5 to 0.75 and the viscosity of the seed oil reduces from 2169 to 362 mm^(2)/s.The linseed oil and its biodiesel exhibited similar trend of reduced viscosity at higher shear rate,however,linseed biodiesel demonstrated the lowest viscosities,cloud points and pour points owing to reduced fatty contents.The effect of the linseed oil and its biodiesel on the pour point and cloud point of the waxy crude oil was determined;and the performance compared to that of xylene.A rapid drop in the pour point and cloud point was observed with the wax crude pre-heated with 0.1 v/v linseed oil,its biodiesel and xylene.