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.     

大民屯凹陷高凝油低凝油特征及其分布规律

高凝油为高含石蜡、地蜡的石蜡基原油,含蜡量>30%,凝固点高达40—69℃,为成熟的原生未氧化原油,低凝油为负凝固点原油,具“四高三低”特征,最低凝固点可达-40℃,属次生细菌降解原油,高凝油分布受沙四源岩和早期断裂所控制;低凝油受沙三源岩和稀油原油所控制,东营期断裂活动为其聚集和降解提供了良好前提。      

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.     

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.     

Correlations Between the Pour Point/Gel Point and the Amount of Precipitated Wax for Waxy Crudes

The amount of precipitated wax is one of the key factors that governs the flow properties of waxy crudes. Experimental results of 24 crudes have shown that approximately 2 wt% precipitated wax is sufficient to cause a virgin waxy crude gelling. Accordingly, a correlation between the pour point and the temperature at which 2 wt% of wax has precipitated out from a crude oil; i.e., T_c(2 wt%), and a correlation between the gel point and T_c(2 wt%) have been developed. The proposed correlation of the pour point is in accordance with the correlation developed by Letoffe et al. (1995) on the basis of 14 crudes from eight countries. The development of the gel point correlation and further verification of the pour point correlation indicate that there is a relationship between the gelling of virgin waxy crudes and the amount of precipitated wax. According to these correlations and the amount of precipitated wax, which can be determined only with a little sample by thermodynamic models or Differential Scanning Calorimetry (DSC) experiment, the gel point and pour point of virgin waxy crude can be predicted even if the oil sample is very limited. Heat treatment and chemical treatment can greatly improve flow behavior of waxy crudes, and more precipitated wax is present when the beneficiated (thermally beneficiated or PPD-beneficiated) crude oils gel. Experimental results showed that approximately two or three times the amount of precipitated wax presents at the gelling temperature when the oils were in their beneficiated (thermally beneficiated or PPD-beneficiated) conditions.     

防蜡剂SZ－3及其性能特点

为了解决胜利桩西油田高含蜡原油开采中的严重结蜡问题，研制了ＳＺ－３防蜡剂。该剂为以ＥＶＡ甲苯溶液为内相，水为外相，含有油溶性和水溶性非离子表面活性剂和低分子醇的Ｏ／Ｗ乳状液，从油套环空投入采油井井底，防蜡效果良好。本文介绍了该剂的研制、配方、室内性能测定和现场试验简况。     

Poly(ethylene-co-vinyl acetate) (EVA) as wax inhibitor of a Brazilian crude oil: oil viscosity, pour point and phase behavior of organic solutions

Several techniques have been used to minimize the problems caused by the wax deposition, and the continuous addition of polymeric inhibitors is considered an attractive technological alternative. The addition of copolymers like polyacrylates, polymethacrylates or poly(ethylene-co-vinyl acetate) (EVA) permit to inhibit the deposition phenomenon; nonetheless, this effect is specific, i.e. similar copolymers present different performance depending on their physical–chemical properties in solution. In this work, the influence of the EVA vinyl acetate content on the viscosity and the pour point of a Brazilian crude oil were evaluated. A correlation between both results was also obtained. The phase behavior and the solubility parameter of EVA copolymers, with different vinyl acetate contents, were investigated in various solvents together with an evaluation of the efficiency of these copolymers as pour point depressants for two different samples of crude oil. EVA copolymers containing 20, 30, 40 and 80 wt.% of vinyl acetate were used and tests with the crude oil were carried out using 50, 500, 1000 and 5000 ppm of EVA as additive. The results obtained from viscosity measurements showed that only below the temperature at which wax crystals start forming did the copolymer exhibit a strong influence in the reduction of oil viscosity, at an optimum concentration. The pour point results revealed EVA 30 to be the most efficient. The results obtained from both experiments showed that the viscosity and the pour point behaviors do not show good correlation. Not only the solubility parameter and the vinyl acetate content, but also the molecular weight and polydispersity have an important influence on both phase behavior and pour point depression. Furthermore, it was confirmed that the additive must present a reduced solubility at a temperature close to the crude oil cloud point. This, however, is not the only factor that determines the efficiency of the additive as paraffin/wax deposition inhibitor.     

An empirical correlation for estimating the viscosity of non-Newtonian waxy crude oils

Non-Newtonian fluids are the most complex ones when it comes to predicting their flow behavior. In the pre-existing models, rheological behavior in waxy crude oils is mainly affected by shear rate and thermal history of crude oils. In the present work, rheological characteristics of four different crude oils were studied by coaxial cylindrical rheometer at three different temperatures (40°C, 50°C, and 60°C) and a model was proposed keeping into consideration wax content for the first time. This model is prepared to predict the viscosity of four different crude oils with different wax content and at different temperature. The proposed model can efficiently estimate the viscosity as compared to other established models.     

Wax Deposition in Flow Lines Under Dynamic Conditions

The wax deposition in the tubing, pipeline, and surface flow line is the major problem in the oil fields. It generates additional pressure drop and causes fauling and ultimately increases the operating cost during production, transportation, and handling of waxy crude oil. In this work, attempts were made to study the wax deposition in the flow lines due to Indian crude oil under dynamic condition. The experimental work was carried out for neat crude oil and pour point depressants treated crude oil at different ambient/surface temperature and pumping/reservoir temperature. It was observed that temperature has significant effect on the wax deposition of the crude oils. From these studies, ideal temperature of crude oil to pump in the pipeline or flow line was determined. The present investigations also furnishes that the selected pour point depressant in this work decreases the wax deposition significantly and may be used for controlling the wax deposition problems in case of Indian crude oil.     

高凝油渗流特性的实验研究

选择２块人造岩心和２块取自于沈北油田的天然岩心，分别在不同条件下饱和地层水，进行了油驱水实验，实验用油具有较高的含蜡量和凝固点；由实验观察可知，温度是决定高凝油渗流特性的决定性因素，当温度高于反常点时，原油呈牛顿流体，粘度在整个渗流过过程不变，反之则呈非牛顿流体，粘度对温度非常敏感，随温度降低，原油粘度升高，油相渗透率和驱油效率降低，在析蜡前后，变化尤为明显；高凝油的渗流特征还受压力梯度的影响，最     

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.     

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.     

聚合物/微纳米复合含蜡原油降凝剂的研究进展

含蜡原油中蜡分子的结晶析出会使原油的低温流变性显著恶化,降低原油管输的安全性和经济性.添加少量的聚合物型降凝剂能够改变蜡分子的结晶习性,改善原油的宏观流动性.加降凝剂原油的凝点越低、低温黏度越小,意味着输送的能耗越低、安全性越高,因此人们对原油降凝剂的降凝降黏效果追求是无止境的.利用不同的微纳米颗粒,研制高效的聚合物/...     

The Formation of Waxy Crude Oil-in-water Emulsions for the Reduction of Pour Point and Viscosity

Waxy crude oil is characterized by high pour point and poor flow properties, which bring great difficulty to the oil exploitation and transportation. In this study, the fluidity of waxy crude oil with the pour point of 47°C was highly improved by emulsification with synthetic formation water used as aqueous phase. It was found that the combination of CAO-35 and sodium oleate was an effective emulsifier mixture to form stable waxy crude oil-in-water emulsion and when the mass ratio of oil to water was 7:3, the optimum composition of emulsifying additives with respect to the total mass of the emulsion was obtained as follows: emulsifier mixture (the mass ratio of CAO-35 to sodium oleate was 8:2) 0.4% (w/w), sodium triphosphate 0.028% (w/w), NaOH 0.05% (w/w), and polyacrylamide 0.15% (w/w). Diverse factors affecting the pour point of the formed emulsion were also studied. It was found that the pour point of emulsion increased as oil content increased and the optimum mixing speed and cooling rate were 600 rpm and 0.5°C/min, respectively. Under the optimum emulsifying conditions, when mixing speeds were 250 and 600 rpm, respectively, by forming O/W emulsions with the oil content of 70%, the pour point reductions were 20 and 25°C, respectively, and the corresponding viscosity reductions were 89.79% and 97.46% (40°C), respectively. Thus the pour point and viscosity of waxy crude oil are obviously reduced by forming oil-in-water emulsion, which is highly promising for the exploitation and transportation of waxy crude oil.     

Polyoctadecylacrylate (POA) and resin-stabilized asphaltene synergistically improve the flow behavior of model waxy oils

In this paper, the effect of POA PPD together with resin-stabilized asphaltenes on the flow behavior of model waxy oils was investigated through rheological test, DSC, microscopic observation and asphaltenes precipitation test. Compared to the POA or asphaltenes alone, POA/asphaltenes cannot further decrease the wax appearance temperature of oils, but can dramatically decrease the pour point, gelation point, G′, G″ and apparent viscosity of oils. POA molecules can adsorb on the surface of asphaltenes, thus inhibiting the asphaltenes precipitation and forming the POA/asphaltenes composite particles. The composite particles can act as wax crystallization templates and then greatly change the wax crystals' morphology into large and spherical-like, thus improving the waxy oil flow behavior.     

蜡晶形态结构对原油降凝的影响

 采用偏光显微镜观察了不同条件下蜡晶的形态变化，对蜡结晶过程中的结构、分布状态和生长规律进行了深入的研究，采用气相色谱分析了用52#、62#、80#蜡配制的模拟油中蜡的碳数分布，考察了凝点与蜡含量之间的变化规律，以及沥青质、胶质和大分子降凝剂(PPD)对模拟油降凝、降粘的影响，为改善原油流动性提供理论依据。实验结果表明，蜡晶的微观形态结构、蜡在油中的溶解性能以及降凝剂的降凝作用与模拟油中蜡的碳数分布密切相关，只有当降凝剂分子结构与油中蜡的结构匹配时，才能达到理想的降凝效果。通过实验确定了模拟油降凝时的临界蜡含量为40%（质量分数），大于该临界值后，凝点随着蜡含量的变化幅度将大大降低。     

Evaluations of the effect of selected wax inhibitive chemicals on wax deposition in crude oil flow in sub-sea pipe-lines

Comparative studies were made on the effect of different wax inhibitive chemicals on the wax deposition volume during crude oils flow in pipeline. Two crude oils from Ovhor and Jisike oil fields in the southern part of Nigeria were used in the study. The four identified chemicals: Alkyl sulphonates (wax dispersant), polyethylene (wax inhibitors/crystal modifier), acrylate ester copolymer (pour point depressant, PPD) and xylene (wax solvents) inhibit wax deposition to varying degree of between 14.6–44.9% for crude oil A, and between 21.6–41.4% for crude oil B when 1500 ppm of each chemical was mixed with the crude oil sample. The optimal wax inhibition formulation of polyethylene, xylene, acrylate ester polymer and alkyl sulphonate contains 40.4, 19.2, 27.6, 12.8% and 36.3, 21.5, 25.8, 16.4% for crude oil A and B respectively. Applications of the optimal formulated mixtures of the above chemicals inhibit wax deposition by 58.9% and 62.4% for crude oil A and B respectively.     

LOW TEMPERATURE FLOW CHARACTERISTICS OF SOME WAXY CRUDE OILS IN RELATION TO THEIR COMPOSITION : PART I WITH AND WITHOUT POUR POINT DEPRESSANT ADDITIVES

The yield stress, plastic viscosity and apparent viscosity and the dependence of the latter on the shear rate have been studied at different temperatures below pour point of Lingala (Krishna-Godavari basin, Eastern coast), Duliajan (Eastern region of Assam), Rava (Godavari basin) and Bombay-High (off-shore western region) indigenous crude oils

Four different commercial pour point depressant additives have been used to study their effects on the pour point, yield stress and plastic viscosity

From this study it has been found that wax concentration and its composition are primarily responsible for the variation in the pour point, and crude base composition has a small effect. However, the response of the pour point depressant additive in effecting the change in the pour point is primarily governed by the liquid matrix. As the temperature is lowered both the yield stress and plastic viscosity increase in case of each crude oil. However, the magnitude is dependent on the nature of the crude oil. With pour point depressant additives, the yield stress and plastic viscosity are decreased and this decrease is a function of nature of the liquid matrix of the crude oil and concentration of the additive     

EVA加剂量对含沥青质蜡油流变性的改善效果

通过流变实验、差示扫描量热分析以及显微观察，探究了乙烯-醋酸乙烯酯共聚物(EVA)质量分数对含沥青质蜡油流变性改善效果的影响，并揭示了EVA与沥青质协同降凝降黏机理。结果表明，单独添加EVA或沥青质可在一定程度上改善纯蜡油的低温流变性，且随着EVA质量分数的增大，蜡油的凝点不断降低，低温流变性逐渐变好，在EVA质量分数为1000 mg/kg时，蜡油凝点由加剂前的35 ℃降为20 ℃，15 ℃时的表观黏度由870.2 mPa·s降到229.6 mPa·s。EVA和0.75%质量分数的沥青质能够产生良好的协同作用，进一步改善蜡油的低温流变性，且随着EVA质量分数的提高，协同效果呈现先变好后变差的规律，并在EVA质量分数为100 mg/kg时取得最佳的协同降凝降黏效果，此时析出的蜡晶可形成尺寸最大、结构最致密的蜡晶絮凝体，蜡油凝点降低至-20 ℃以下，黏弹性参数与表观黏度也大幅度降低；进一步增大EVA加剂量导致协同效果变差，凝点、黏弹性参数和表观黏度都略有回升。