A new experimental investigation on upgrading of waxy crude oils by methacrylate polymers

Several methods have been used to reduce problems caused by wax precipitation during the production and/or transportation of waxy crude oil. Polymers are used to improve pour point and rheological behavior of waxy crude oils. In this work, the influence of the polymer inhibitors such as methacrylate polymers, as wax inhibitor, with different range of molecular weight and alkyl side chain carbons on the rheological behavior and pour point of two Iranian waxy crude oils were evaluated. Two Iranian waxy crude oils were selected on the basis of wax and asphaltene contents. The rheological behavior of these crude oils in absence and in presence of methacrylate polymer was studied. The rheological data cover the temperature range of–1 to 12°C. The results indicated that the performance of methacrylate polymer was dependent on the molecular weight, alkyl side chain carbons and the asphaltene content of crude oil. Methacrylate polymers with longer alkyl side chains than 18 carbons would perform best as wax inhibitors in two cases. Also, for crude oil with low asphaltene, higher molecular weight methacrylate polymer is the best flow improver and lower molecular weight methacrylate polymer showed good efficiency for crude oil with high asphaltene content.     

Characteristic Temperatures of Waxy Crude Oils

Gel point or pour point is widely used to evaluate the low temperature flowability of crude oil. However, it is not adequate to describe the gelling properties of waxy crude oils under flow conditions with gel point or pour point, since the rheological behavior of crude oils is dependent on shear history. Waxy crude oils tend to gel at a low temperature. Based on gelation theory, the characteristic temperature of waxy crude oil was determined by analyzing viscosity-temperature data. Two mathematical models were developed for calculating characteristic temperatures of virgin crude oils and pour point depressants (PPD) beneficiated crude oils, respectively. By using these two models, the characteristic temperatures of crude oils that have experienced shearing and thermal histories can be predicted. The model for predicting the characteristic temperature of virgin crude oils has an average relative deviation of 4.5%, and all predicted values have a deviation within 2 ℃. Tested by 42 sets of data, the prediction model for crude oil treated with PPD has a high accuracy, with an average relative deviation of 4.2%, and 95.2 percent of predicted values have a deviation within 2 ℃. These two models provide useful ways for predicting the flowability of crude oils in pipelines when only wax content, wax appearance point and gel point are available.     

Experimental study and a proposed new approach for thermodynamic modeling of wax precipitation in crude oil using a PC-SAFT model

A powerful method is necessary for thermodynamic modeling of wax phase behavior in crude oils,such as the perturbed-chain statistical associating fluid theory(PC-SAFT).In this work,a new approach based on the wax appearance temperature of crude oil was proposed to estimate PC-SAFT parameters in thermodynamic modeling of wax precipitation from crude oil.The proposed approach was verified using experimental data obtained in this work and also with those reported in the literature.In order to compare the performance of the PC-SAFT model with previous models,the wax precipitation experimental data were correlated using previous models such as the solid solution model and multi-solid phase model.The results showed that the PC-SAFT model can correlate more accurately the wax precipitation experimental data of crude oil than the previous models,with an absolute average deviation less than 0.4 %.Also,a series of dynamic experiments were carried out to determine the rheological behavior of waxy crude oil in the absence and presence of a flow improver such as ethylene–vinyl acetate copolymer.It was found that the apparent viscosity of waxy crude oil decreased with increasing shear rate.Also,the results showed that the performance of flow improver was dependent on its molecular weight.     

原油乳状液稳定性研究：Ⅶ.蜡晶对油水界面膜性质的影响

对分别含有大庆,吉原油界面活性组分的航空煤油与蒸馏水及模拟地层水在不同温度下的界面粘度,界面膜屈服值进行了测定。结果发现,由于吉林原油界面活性组分含有较多的蜡晶,当温度较低时,随温度升高,吉林模型油界面粘度逐渐升高,界膜表现为负触变性;     

The action mechanism of wax inhibitors (WI) on pour point and viscosity of mixed waxy oil

Several methods had been used to minimize the problems caused by wax deposition in crude oil pipelines during the production and transportation of waxy crude oil; among them, the continuous addition of wax inhibitor (Abbreviation for WI) is considered as the most efficient one. This study uses two kinds of polymeric compounds as wax inhibitors with different solvents on the pour point and viscosity of mixed waxy oils evaluated. These four wax inhibitors defined as WI-1, WI-2, WI-3, WI-4, respectively. Five types of mixed waxy oil have the same wax content but different resin contents. Meanwhile, different resin contents affect the pour point and viscosity of mixed oils. Under different processing temperature, the viscosity of mixed oil measured when the temperature changes among 20 to 60°С. In this work, the results were that the effect of WI-1 and WI-3 relied on the resin content, processing temperature and dosing concentration. For mixed waxy oils, the pour point reductions contacted with dosing concentration and the resin content. The wax inhibitor shows good efficiency when the resin content was between 1.01 and 4.03 wt %. When the WI-1 added, the pour point of mixed oil-1 reduced 30°С at most and viscosity of mixed waxy oil greatly reduced. In sum, toluene as solvent shows better performance of wax inhibitors.     

The Pressure Effect on Rheological Behavior of Water Content of Waxy Crude Oil

Abstract

The viscosity of waxy crude oil and oils with different water contents from Bohai Sea oilfield with different temperature, pressure, and shear rate was studied. The relationship between viscosity and temperature or pressure fit well to the exponential law. The wax appearance temperature (WAT) at high pressure was also studied. The WAT increased linearly with pressure, and the slope was about 0.1°C/MPa. The maximum deviation of the WAT with different water contents was 0.5°C when the pressure changed from 0.1 to 12 MPa and this demonstrates that water content had little effect on the WAT of Bohai Sea crude oil.     

Rheological and physicochemical characterization of UAE crude oil

This study focuses on the rheological and physiochemical characterization of three samples of light crude oil and fuel oil from the United Arab Emirates. The dependence of density on temperature ranging from 20 to 200°C was determined. Also, the impact of temperature was investigated on viscosity, shear stress τ, shear rate, yield stress, and thixotropic behavior, and characterized by the Haake RheoStress. The exponential decrease of viscosity over temperature range was modeled using Arrhenius equation. The shear stress–viscosity data revealed that crude oil A solely exhibited Newtonian behavior while crude oils B and C and fuel oil followed the Herschel-Bulkley model.     

Experimental investigation of the rheological behavior of algerian crude oils from the quagmires

In this work, the rheological behavior for three types of crude oil coming from different quagmires namely Amassak, Tamendjelt and Tin Fouye of the TFT sector (Tin Fouye Tabankort/South Algeria) has been experimentally investigated. A controlled stress rheometer (AR 2000, TA Instrument) was used throughout this investigation. The experimental measurements in terms of flow and dynamic tests were carried out at different temperatures during the shear rate over the range of 0–700?s^?1 and frequency range of 0.1–10?rad/s. The obtained results show that the viscosity and shear stress of the crude oils decreases about 53.30%, 58.80%, and 59% respectively, when the temperature increased from 10 to 20?°C. The yield stress required to flow of crude oils also decreased to 37.06%, 89.78%, and 77.53% respectively. The dynamic analysis of the crude oils by identifying of the storage modulus (G′) and the loss modulus (G″) has indicated that the rheological properties of crude oils were significantly temperature-dependent.     

Rheological properties of crude oils with a high resin and asphaltene content. Effect of an electromagnetic field and modifiers

The rheological properties of crude oils from the Kuchukov field were investigated at 20–70°C in the presence of surfactants and after treatment with a high-frequency electromagnetic field. The viscosity of crude from one field is a function of the resin and asphaltene content. Addition of ethylene glycol diglycidyl ether improves the rheological characteristics. __________ Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 3, pp. 34–35, May–June, 2006.     

Investigating the rheological behavior of Algerian crude oil stemming from station of separation (quagmire)

An experimental study was conducted to investigate the rheological behavior of Algerian crude oil stemming from station of separation (quagmire) of the Tin Fouye Tabankort sector (southern Algeria). The rheological measurements at different temperatures (20°C, 30°C and 50°C) were performed employing AR 2000 rheometer of TA-Instruments. Several parameters such as shear rate, the temperature and the presence of crude oil from another quagmire on the rheological properties have been studied. The experimental results show that the studied crude oil displays non-Newtonian shear thinning behavior at low values of shear rate and a Newtonian behavior at high values of shear rate, which can be best presented by the Casson model. The rheological examination tests (flow and dynamic mode (oscillation)) have shown that the rheological properties of the crude oil were significantly influenced by the temperature and the crude oil addition.     

An Experimental Study of Rheological Properties of Nigerian Waxy Crude Oil

Abstract

Nigerian crude oils are known for their good quality (low sulfur, high American Petroleum Institute gravity). However, similar to any other paraffinic-based crudes, most Nigerian crudes contain moderate to high contents of paraffinic waxes. These waxy crudes exhibit non-Newtonian flow behavior at temperatures below the cloud point because of wax crystallization. In order to accurately predict flowing and static temperature profiles, design waxy crude oil pipelines, evaluate flow interruption scenarios, and start up requirements in the handling of waxy crude oils, the effect of temperature and shear rate on the rheology of crude oils must be determined. This work presented some experimental results on the rheology of two waxy crude oils produced from different Nigerian oil fields. A Brookfield DV-III ultraprogrammable rheometer (Brookfield Engineering Laboratories, Middleboro, MA) was utilized. The temperature dependence of rheological properties and thixotropy of these crudes were investigated. The influence of some petroleum-based diluents to depress the wax appearance temperature (WAT), their effect on the thixotropic/yield pseudoplastic behavior of two Nigerian crudes were studied and it was observed that lower wax content crude has higher tendency to regain its cohesive lattice bonding (yield strength) when left undisturbed for some days at its gel point after agitation. The experimental results showed that the addition of petroleum-based diluents to the lower wax content crude oil leads to its lost some of its yield strength regaining capacity.     

KINEMATIC VISCOSITY-TEMPERATURE BEHAVIOR OF HEAVY TBP-FRACTIONS (455°C+) OF ARABIAN CRUDE OILS

ABSTRACT

A generalized kinematic viscosity-temperature correlation for undefined liquid heavy petroleum fractions has been developed to represent the data for a wide range of temperature from 100°C to 200°C. The correlation is based on the experimental kinematic viscosity data of true boiling point fractions of four Arabian crude oils. The characterization property required for estimation is 50% boiling point. The proposed correlation fits the experimental data with an overall absolute error of 6.1%. Experimental measurements of kinematic viscosity of heavy true boiling point fractions of Arabian crude oils were also obtained in order to develop the proposed correlation.     

Rheological Properties and Composition of Some Vacuum Distillates Derived from Indian Crudes

Abstract

Three vacuum distillates boiling range 400°C–530°C derived from Bakrola, Dholka, and PY-3 crudes of Gujarat region (India) were subjected to urea adduction to isolate n-paraffin components from them. The deparaffinized base oils obtained after removal of n-paraffin components from the distillate fractions were further fractionated into various hydrocarbon-type constituents viz iso + cyclo paraffins, aromatics, and polar components by column chromatography. The influence of various hydrocarbon-type components thus separated on rheological characteristics (pour point and viscosity temperature behavior) of deparaffinized base oil was investigated. This study was done by preparing base oil blends by adding separated hydrocarbon-type constituents in various concentrations to different base oils and characterizing them. The effect of change of solvent matrix on the rheological characteristics was also determined. The study demonstrated the role of solid n-paraffins for variation in pour point and viscosity temperature behavior of the waxy distillate fractions.     

LOW TEMPERATURE FLOW CHARACTERISTICS OF SOME WAXY CRUDE OILS IN RELATION TO THEIR COMPOSITION : PART II EFFECT OF WAX COMPOSITION AND CONCENTRATION ON THE DEW AXED CRUDE OILS WITH / WITHOUT ADDITIVES

ABSTRACT

In this part of the work the effect of wax concentrations on the rheologica! properties of the dewaxed Duliajan (Assam) and Lingaia crude oils have been studied. The dewaxing of the crude oil was done by removing n-paraffins from the crude oil by urea adduction. The urea adducted n-paraffins concentrate-the wax- was characterized by its carbon number distribution. The urea non adducted oil portion - the denormalized crude oil (DNO)- was characterized for its pour point. The wax in different concentration was then added in the DNO and the change in the rheological properties like pour point, yield stress and plastic viscosity were studied using a Haake Rota Viscometer. The effect of carbon number distribution, i.e. the composition of the wax, on these rheological properties was also investigated. Four different commercial pour point depressanl additives have been used to study their effects on the pour point, yield stress and plastic viscosity of the reconstituted (wax mixed DNO) crude oils.

From this study it has been found that wax concentration and its composition are primarily responsible for the variation in the pour point of the DNO, and the DNO composition has a small effect. However, as seen in the Part I of this paper, the response of the pour point depressant additive in effecting the change in the pour point is primarily governed by the composition of the DNO. The additives have shown better response in the DNO having more aromatic concentrate, as has been found in the case of Duliajan (Assam) DNO.     

普适性结蜡模型研究

根据原油在管道内流动特性及析蜡规律,提出了有效析蜡量的计算方法.利用F检验法筛选了原油结蜡的主要影响因素,包括原油黏度、管壁处剪切应力、温度梯度及管壁处蜡晶溶解度系数.利用9种原油室内环道结蜡实验数据,按照逐步线性回归的方法,得到了含蜡原油的普适性结蜡模型.该模型不需进行结蜡模拟实验,只需根据原油的黏度、析蜡特性及密度等物性参数就可预测原油的结蜡规律.在未进行室内结蜡模拟实验的情况下,利用普适性结蜡模型预测了中宁-银川输油管道不同工况下沿线结蜡分布,并和现场运行参数进行了对比,平均误差为6.32%,最大误差为20%,预测结果为现场清管作业提供了依据.     

Rheology of Middle Distillate. I. Role of Composition

Abstract

The rheological behavior of middle distillate (250–375°C) fraction, obtained from the waxy Bombay-High Off-shore crude oil, and its five narrow sub-fractions of 25°C interval each, i.e., Fr 1 (250–275°C), Fr 2 (275–300°C), Fr 3 (300–325°C), Fr 4 (325–350°C), and Fr 5 (350–375°C), have been studied below their ASTM pour point temperatures. The rheograms (the shear stress vs. rate of shear) of the fraction and sub-fractions, at various temperatures below their pour points, are recorded on a Haake RV-12 Co-axial Rota Viscometer fitted with a NV sensor and a temperature programmer (PG-20) and attached with a programmed heating/cooling system. From these rheograms the flow parameters like plastic viscosity, apparent viscosity, and yield stress are obtained and their variations with temperature and shear rate have been studied in terms of compositions of the fraction/sub-fractions. These results might be useful in devising methodology for overcoming the wax separation phenomenon from middle distillates at low temperatures.     

A Study on Creep Behavior of Gelled Daqing Crude Oil

Abstract

Gelled waxy crude oils have complex rheological properties. Experimental research and mechanical analogy were performed for the creep behavior of Daqing crude oil. The experienced stages in creep process were partitioned based on the changes of strain and strain rate with the increasing loading time. When the loading stress was lower than the yield stress, there existed three stages; namely, instant elastic deformation, decelerated creep, and constant rate creep. When the applied stress was higher than the yield stress, accelerated creep occurred after the above three stages. By applying mechanical analogy, the elastic element, viscous element, plastic element, and accelerated creep element were employed to reflect the interior strain mechanism of crude oil under creep condition. A creep equation was proposed by incorporation with the analysis on the creep experiment. Based on the creep equation, nonlinear regression was conducted by using the creep experiment data of Daqing crude oil at different temperatures of 28°C, 29°C, 30°C, and 31°C, respectively. The average correlation coefficient was 0.9907. Substituting the calculated equation parameters into the creep equation, the creep behavior under other shear stresses can be predicted at the same temperatures. The average relative deviation is 8.29%. The change of strain of crude oil before yielding can be accurately described by the creep equation.     

Rheological behaviour of crude oil: Effect of temperature and seawater

The effect of temperature and seawater on rheological behavior was investigated in this work for four samples of crude oil from Algerian Sahara. The Newtonian model was used to fit the shear stress dependence on the shear rate for temperature range between 20 and 100°C. The temperature increase leads to a decrease in the dynamic viscosity of crude oil. The temperature dependence of dynamic viscosity was fitted by the Walther equation. For crude oil emulsion, the Herschel-Bulkley model was used to fit the shear stress dependence on the shear rate for volume fraction of seawater between 30 and 70%. The increase in the volume fraction of seawater induces not only an increase in the yield stress and the consistency index of crude oil emulsions but also a decrease in the flow index of crude oil emulsions.     

LOW TEMPERATURE FLOW CHARACTERISTICS OF SOME WAXY CRUDE OILS IN RELATION TO THEIR COMPOSITION : PART II EFFECT OF WAX COMPOSITION AND CONCENTRATION ON THE DEW AXED CRUDE OILS WITH / WITHOUT ADDITIVES

In this part of the work the effect of wax concentrations on the rheologica! properties of the dewaxed Duliajan (Assam) and Lingaia crude oils have been studied. The dewaxing of the crude oil was done by removing n-paraffins from the crude oil by urea adduction. The urea adducted n-paraffins concentrate-the wax- was characterized by its carbon number distribution. The urea non adducted oil portion - the denormalized crude oil (DNO)- was characterized for its pour point. The wax in different concentration was then added in the DNO and the change in the rheological properties like pour point, yield stress and plastic viscosity were studied using a Haake Rota Viscometer. The effect of carbon number distribution, i.e. the composition of the wax, on these rheological properties was also investigated. Four different commercial pour point depressanl additives have been used to study their effects on the pour point, yield stress and plastic viscosity of the reconstituted (wax mixed DNO) crude oils.

From this study it has been found that wax concentration and its composition are primarily responsible for the variation in the pour point of the DNO, and the DNO composition has a small effect. However, as seen in the Part I of this paper, the response of the pour point depressant additive in effecting the change in the pour point is primarily governed by the composition of the DNO. The additives have shown better response in the DNO having more aromatic concentrate, as has been found in the case of Duliajan (Assam) DNO.     

Investigation of non-Newtonian flow characterization and rheology of heavy crude oil

The heavy crude oil exhibits a non-Newtonian shear thinning behavior over the examined shear rate. The viscosity of the heavy crude oil decreases about 15.6% when the temperature increased from 30 to 60°C. Heavy crude oil was blended with the aqueous solution of surfactant and saline water in different volumetric proportions of NaCl, and Na₂CO₃ solution mixtures. The addition of 50% of the mixture to the heavy crude oil causes a strong reduction in the viscosity, about 67.5% at 60°C. The heavy crude oil fits the Power law model since it has the lowest average absolute percent error of 0.0291. The flow behavior index of the heavy crude oil reaches a value of 0.9305 at a temperature of 30°C and it increases to 0.9373 when the temperature raises 60°C, while the consistence coefficient decreases from 2.8811 to 2.3558.