Experimental study on wax deposition of highly paraffinic oil in intermittent gas-oil flow in pipelines

Oil-gas two phase wax deposition is a fairly common and open-ended question in flow assurance of multiphase transportation pipelines.This paper investigated the two main aspects of oil-gas two phase wax deposition layer:apparent thickness and crystal structure characteristics.A typical highly paraffinic oil in Bohai Sea,China,was used as the experimental material to investigate the wax deposition thickness in oil-gas two phase under the influence of different oil temperatures,superficial gas/liquid phase velocities and gas-oil ratios by using multiphase flow loop experimental device.Just as in the classical theory of wax molecular diffusion,it showed that wax deposition thickness of oil-gas two phase increased with increasing oil temperature.Analysis of the impact of different superficial phase velocities found that the actual liquid flow heat transfer and shear stripping was the gas phase dominant mechanisms determining wax deposit thickness.In addition,the crystal structure of the wax deposition layer was characterized with the help of small-angle X-ray scattering(SAXS)for different circumferential positions,flow rates and gas-oil ratios.The bottom deposition layer had a complex crystal structure and high hardness,which were subject to change over flow rate variations.Furthermore,the SAXS results provided evidence that the indirect effect of the actual liquid velocity modified by the gas phase was the main mechanism.Our study of the effect of gas phase on the wax deposition of oil-gas two phase will help shed light onto the mechanism by which this important process occurs.Our findings address a very urgent need in the field of wax deposition of highly paraffinic oil to understand the flow security of oilgas two phase that occurs easily in multiphase field pipelines.

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.

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.

An Experimental Study on the Interaction between Hydrate Formation and Wax Precipitation in Waxy Oil-in-Water Emulsions

The coupled formation of wax crystals and hydrates is a critical issue for the safety of deep-sea oil and gas exploration and subsea transport pipeline flow.Therefore,this paper conducts an experimental study on the characteristics of methane hydrate formation in a water-in-oil(W/O)system with different wax crystal contents and explores the influence of different initial experimental pressures on the induction period and maximum rate of hydrate formation.The wavelet function was introduced to process the reaction rate and calculate the maximum speed of hydrate formation.Notably,the higher the pressure,the smaller the maximum rate of hydrate formation.We observed that wax crystal precipitation increases the viscosity of the emulsion,which limits the diffusion of gas in the liquid phase during hydrate nucleation and thus delays the hydrate nucleation.The methane gas precipitation also affects the remaining fraction’s wax content and therefore affects the wax precipitation.Secondary hydrate formation was observed several times during the experiment,increasing the risk of pipeline blockage.Overall,this work provides insights into the effect of wax crystal precipitation on hydrate behaviour that could facilitate flow assurance applications in subsea multiphase pipelines and inform the safe transportation of oil and gas pipelines.

Prediction Model Based on the Grey Theory for Tackling Wax Deposition in Oil Pipelines

Problems involving wax deposition threaten seriously crude pipelines both economically and operationally. Wax deposition in oil pipelines is a complicated problem having a number of uncertainties and indeterminations. The Grey System Theory is a suitable theory for coping with systems in which some information is clear and some is not, so it is an adequate model for studying the process of wax deposition. In order to predict accurately wax deposition along a pipeline, the Grey Model was applied to fit the data of wax deposition rate and the thickness of the deposited wax layer on the pipe-wall, and to give accurate forecast on wax deposition in oil pipelines. The results showed that the average residential error of the Grey Prediction Model is smaller than 2%. They further showed that this model exhibited high prediction accuracy. Our investigation proved that the Grey Model is a viable means for forecasting wax deposition. These findings offer valuable references for the oil industry and for firms dealing with wax cleaning in oil pipelines.

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.

Crude oil wax:A review on formation,experimentation,prediction,and remediation techniques

Wax deposition during crude oil production,transportation,and processing has been a headache since the early days of oil utilization.It may lead to low mobility ratios,blockage of production tubing/pipelines as well as fouling of surface and processing facilities,among others.These snags cause massive financial constraints increasing projects’turnover.Decades of meticulous research have been dedicated to this problem that is worth a review.Thus,this paper reviews the mechanisms,experimentation,thermodynamic and kinetic modeling,prediction,and remediation techniques of wax deposition.An overall assessment suggests that available models are more accurate for single than multi-phase flows while the kind of remediation and deployment depend on the environment and severity level.In severe cases,both chemical and mechanical are synergistically deployed.Moreover,future prospective research areas that require attention are proposed.Generally,this review could be a valuable tool for novice researchers as well as a foundation for further research on this topic.

Prediction of wax precipitation region in wellbore during deep water oil well testing

During deep water oil well testing, the low temperature environment is easy to cause wax precipitation, which affects the normal operation of the test and increases operating costs and risks. Therefore, a numerical method for predicting the wax precipitation region in oil strings was proposed based on the temperature and pressure fields of deep water test string and the wax precipitation calculation model. And the factors affecting the wax precipitation region were analyzed. The results show that: the wax precipitation region decreases with the increase of production rate, and increases with the decrease of geothermal gradient, increase of water depth and drop of water-cut of produced fluid, and increases slightly with the increase of formation pressure. Due to the effect of temperature and pressure fields, wax precipitation region is large in test strings at the beginning of well production. Wax precipitation region gradually increases with the increase of shut-in time. These conclusions can guide wax prevention during the testing of deep water oil well, to ensure the success of the test.

Development of Palm Oil Based Bio-product Industrial Wax and Its Application Performance Study

Machining is a mechanical process where excess material from a work is removed to produce a product. At the moment different ferrous, non-ferrous materials and industrial blue wax have been used for prototype models. However such materials is very expensive. Hence an attempt is made to substitute these materials by the palm oil based bio-wax produced in Malaysia. In this research, the authors will analyze and investigate whether there is a possibility to use the palm oil based bio-wax material to substitute with the petroleum based industrial-wax. Experimental analyses are carried out to investigate the capability and the strength of the palm oil based bio-wax material. The matrix blends were prepared of fatty acids from oleo-chemicals, palm oil wax, natural ash fibre and low linear density polyethylene （LLDPE） by stirring and melt-mixing. Sample b!ends are machined with lathe machining process. The sample blends showed there was no built edge formation and good smooth surface production.

Waxes in asphaltenes of crude oils and wax deposits

Composition and molecular mass distribution of n-alkanes in asphaltenes of crude oils of different ages and in wax deposits formed in the borehole equipment were studied. In asphaltenes, n-alkanes from C12 to C60 were detected. The high molecular weight paraffins in asphaltenes would form a crystalline phase with a melting point of 80–90 ℃. The peculiarities of the redistribution of high molecular paraffin hydrocarbons between oil and the corresponding wax deposit were detected. In the oils, the high molecular weight paraffinic hydrocarbons C50–C60were found, which were not practically detected in the corresponding wax deposits.

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.

The extraction and preliminary characterization of paint oil and paint wax

研究漆籽油和漆蜡提取的最佳工艺,进行单因素实验,对不同品种漆油进了红外分析。结果表明：漆蜡的最佳工艺条件是：石油醚（30℃～60℃）作为提取剂,提取温度为50℃,固液比为1∶20,提取时间12h,漆籽皮的目数是大于100目;漆油的最佳工艺条件是：石油醚（30℃～60℃）作为提取剂,提取温度为50℃,固液比为1∶30,提取时间3h,漆籽皮的目数是大于100目。通过萃取所得的漆油在红外图谱上出峰位置基本一致,表明其化学成分基本相同。

扶余油田外围区块生物胶降黏压裂技术试验

扶余油田外围区块原油密度大、黏度高、凝固点高、含蜡量高,采用常规胍胶携砂压裂技术无法有效开采,压裂投产后初期产量较低,达不到效益产能,外围区块基本处于未开发动用状态。为此,研发了生物胶降黏剂体系与压裂工程技术相配套的降黏压裂技术,并进行了实验评价。评价结果显示,该生物胶具有降凝、降黏、防蜡、乳化、驱油等性能,可显著提高原油流动性。现场试验分为生物胶降黏加砂压裂和生物胶降黏不加砂压裂两种技术方式,共在扶余外围及稠油区块累计实施45口井。前置液胍胶造主裂缝+支撑剂+生物胶降黏剂+支撑剂+后置液降黏剂的技术方法应用在新投产的外围及稠油区块,对比老区内部,在储层物性变差的条件下,投产后产油量超设计产能1.6倍,是老区内部的1.4倍。生物胶降黏不加砂压裂技术主要应用在老井二次压裂或多轮次压裂稠油区块或黏度上升井层,同等条件下对比,黏度由压裂前的70mPa·s下降到25mPa·s,增产量是同区块常规压裂的1.3倍。

沥青质对蜡油加氢处理装置运行影响分析

某公司3.2 Mt/a蜡油加氢处理装置催化剂失活速率高达2.16℃/月。经分析发现,原料沥青质含量大幅上涨是导致该装置催化剂快速失活的主要原因。根据沥青质分子模型和催化剂失活原理,对比分析了原料中沥青质质量分数分别在200、500、2800μg/g工况以及氢分压分别在9.0、11.0 MPa下的催化剂失活速率,提出了延长装置运转周期的措施。根据催化剂失活原理,提出对氢分压在中压范围(小于10.5 MPa)的蜡油加氢处理装置,原料沥青质质量分数控制在小于500μg/g,装置运转周期可达到4 a。原料沥青质质量分数降低到300μg/g以下且匹配合适的催化剂级配方案,可达到催化剂表面积炭稳态平衡,实现装置超长周期运行。

B301试验区油井结蜡主控因素及对策

B301试验区位于H盆地,该试验区目前油井结蜡现象严重,防蜡效果较差,防蜡措施有效期较短,无法满足油井防蜡的需要,亟需找到影响油井结蜡的主控因素。针对上述问题,通过室内实验对产出液中的蜡质、胶质、沥青质和机械杂质含量进行测定。利用Olga数值模拟软件对温度、压力、流速进行模拟。研究表明:蜡质、沥青质、机械杂质含量以及温度、流速为影响B301试验区油井井筒结蜡的主控因素,影响程度强弱依次为蜡质、温度、沥青质、机械杂质、流速。研究成果可为B301试验区进一步高效开发提供理论与技术基础,为高含蜡油藏防蜡方法提供参考。

PHT-01/PHC-05组合催化剂在加氢裂化装置的工业应用

在中国石油辽阳石化公司110万t/a加氢裂化装置中,以俄罗斯原油的二次油(减压蜡油和催化柴油的混合油,二者质量比10∶1)为原料,采用中国石油自主开发的PHT-01加氢精制催化剂、PHC-05加氢裂化催化剂及PHT系列加氢保护剂,为最大限度生产重石脑油进行了工业应用,考察了催化剂应用情况、产品性质及其分布。结果表明:催化剂运行中,可同时进行湿法硫化与钝化操作,精制反应器、裂化反应器的平均反应温度分别为367,363℃,比设计值分别低5,15℃,温升比设计值分别低3,4℃;目标产品重石脑油的含硫(氮)量均小于0.5μg/g、溴指数0.755 mg/g、芳潜质量分数47.3%、初馏点73℃、收率51.56%,精制油含氮量为7~9μg/g,主要产品收率为94.04%,满足下游重整装置进料要求。

JH油田含蜡原油析蜡温度测试与分析

采用显微镜观察法、黏温曲线法、DSC法分别测试了JH油田六个不同区块的原油析蜡温度。在DSC法中,测定了降温速率5、10℃/min下的析蜡点。在黏温曲线法中,测定了剪切速率10、20、50、100 s^(-1)下的析蜡点。在显微镜观察法中,测定了降温速率0.5、5℃/min下的析蜡点。实验结果表明,不同方法测量的析蜡点有所差异,一方面与不同测试方法的原理有关,另一方面与仪器的分辨率、操作者的经验有关。若原油中的活性物质和大分子不溶物影响较大时,也会表现不同。

高含蜡原油聚烯烃降凝防蜡剂的合成及性能评价

以丙烯酸十八酯(ODA)、十八烯(ODE)和苯乙烯(SM)为单体合成三元共聚物P(ODA-co-ODE-co-SM),以其为主剂合成了聚烯烃降凝防蜡剂POOS,对三元共聚物的合成条件进行了优化,并对加剂前后原油流变性、析蜡特性、微观形态以及降凝防蜡效果进行了评价。结果表明,三元共聚物最优的合成工艺条件为n(ODA)∶n(ODE)∶n(SM)=5∶3∶2、引发剂过氧化苯甲酰含量(以丙烯酸十八酯、十八烯和苯乙烯总质量为基准,下同)为5‰、反应温度70℃、反应时间8h。当POOS质量浓度为200mg/L时,原油流变性与未加POOS原油相比变化明显,15℃下加剂前后屈服应力为50.30和2.95 Pa,屈服应力降幅为94%,析蜡温度由31.33℃降至24.94℃,凝点由25℃降至15℃,加剂后冷指测试防蜡率为88.00%,环道测试防蜡率为83.70%,蜡晶形态由针状转变为圆状结晶,加剂后蜡晶析出分布不均匀,多个微小蜡晶聚集析出形成单个聚集体,POOS的加入有效改善了蜡晶分散形态,抑制网状结构形成,显著改善了原油低温流动效果。

金龙2井区含蜡原油结蜡微观机理及预测模型

采用分子动力学方法研究了含蜡原油结蜡的微观机理,通过实例优选了结蜡预测模型,根据含水率对结蜡量的影响对预测模型进行修正,并提出考虑原有结蜡厚度对后续结蜡影响的计算流程。实验结果表明,初始蜡分子先在原油中分散,后在非晶细胞盒子中聚集形成蜡晶,随着温度升高径向分布函数峰值降低,蜡分子分布从紧密聚集向分散转变;修正后的结蜡预测模型计算误差仅为4%,随着含水率的增高结蜡厚度减小,随生产时间的延长结蜡厚度增加缓慢。修正后的结蜡预测模型能准确预测金龙2井区清蜡周期,可为现场清防蜡工艺提供理论指导。

油水乳化胶凝作用对蜡沉积影响的定量表征

通过对乳液黏温曲线变化规律进行挖掘,对凝油团形成过程定量表征,推导得出凝油团形成的数学关系表达式,将胶凝过程细化为凝油团形成和黏附两个阶段。通过蜡沉积的温度条件,发现随着沉积管壁的温度降低,凝油团形成系数逐渐增大,胶凝作用逐渐显著,即在沉积初期蜡沉积的厚度迅速增加,这与蜡沉积实验结果相吻合。