A fundamental model of wax deposition in subsea oil pipelines

Wax deposition in subsea pipelines is a significant economic issue in the petroleum industry. A mathematical model has been developed to predict the increase in both the deposit thickness and the wax fraction of the deposit using a fundamental analysis of the heat and mass transfer for laminar and turbulent flow conditions. It was found that the precipitation of wax in the oil is a competing phenomenon with deposition. Two existing approaches consider either no precipitation (the independent heat and mass transfer model) or instantaneous precipitation (the solubility model) and result in either an overprediction or an underprediction of deposit thickness. By accounting for the kinetics of wax precipitation of wax in the oil (the kinetic model), accurate predictions for wax deposition for both lab‐scale and pilot‐scale flow‐loop experiments with three different oils were achieved. Furthermore, this kinetic model for wax precipitation in the oil was used to compare field‐scale deposition predictions for different oils. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

Wax deposition modeling of oil/gas stratified smooth pipe flow

Wax deposition modeling is complicated under oil/gas two‐phase pipe flow and therefore remains poorly understood. One‐dimensional empirical heat and mass transfer correlations are unreliably for deposition modeling in stratified flow, due to non‐uniform deposit across the pipe circumference. A mathematical model has been developed to predict the deposit thickness and the wax fraction of deposit in oil/gas stratified pipe flow using a unidirectional flow analysis of non‐isothermal hydrodynamics and heat/mass transfer. The predictions for wax deposition are found to compare satisfactorily with experimental data with three different oils for single phase and oil/gas stratified pipe flow. In particular, the reason that the deposit forming a crescent shape at the cross section of pipe observed in different experiments is revealed, based on the non‐uniform circumferential distributions of two most important parameters for the wax deposition, diffusivity at oil–deposit interface, and the solubility gradient at the oil–deposit interface at different time. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2550–2562, 2016     

Deposition from waxy mixtures in a flow‐loop apparatus under turbulent conditions: Investigating the effect of suspended wax crystals in cold flow regime

The effect of suspended wax crystals in wax‐solvent mixtures on the solid deposition process in the cold flow regime was investigated experimentally and analyzed with a steady‐state heat transfer model. A bench‐scale flow‐loop apparatus, incorporating a concentric‐cylinder heat exchanger, was used to measure solid deposition, in the cold flow and hot flow regimes, from wax‐solvent mixtures under turbulent flow conditions. The deposition experiments were performed with two wax‐solvent mixtures, at two flow rates, with two coolant temperatures, at 8 wax‐solvent mixture temperatures, and for several deposition times. The role of wax crystals on the deposition process was investigated by repeating some of the deposition experiments with a pre‐filtered wax‐solvent mixture. In all experiments, the deposit was formed rapidly such that a thermal steady‐state was attained within 30 min. The deposit mass increased with decreasing the mixture temperature in the hot flow regime, reached a maximum as the mixture temperature became equal to the WAT, and then decreased linearly to zero in the cold flow regime as the mixture temperature approached the coolant temperature. Also, the deposit mass decreased with an increase in the Reynolds number and the coolant temperature. The data and predictions confirmed the solid deposition to be a thermally‐driven process. The experimental deposit mass results in the cold flow regime, supported by model predictions, were identical for the unfiltered and filtered mixtures, which showed that the suspended wax crystals do not affect the deposit mass or thickness.     

Modelling wax deposition of diesel in sequential transportation of product oil pipeline using optimized back propagation neural network

Contamination of gasoline by wax deposit of diesel is a severe problem in sequential transportation of product oil pipelines in cold areas. However, most works on wax deposition are focused on crude oil. In response, this paper aims to investigate wax deposition from a unique perspective of diesel oil in sequential transportation. To this end, a cold finger apparatus was designed and constructed. It is found that the wax deposition rate of diesel oil increases with oil temperature and wax content, and decreases with cold finger temperature. A non-monotonic variation trend is observed against shear stress. To predict diesel wax deposition rate, a back propagation (BP) neural network optimized by bald eagle search (BES) algorithm is proposed. Grey relational analysis (GRA) is employed to get the highly relevant factors as input parameters of the developed model. Prediction accuracy and generalization ability of the BES-BP model is experimentally verified. This work will be helpful to schedule the transportation program of product oil to avoid contamination of gasoline by diesel wax deposit.     

Study on wax precipitation characteristics of wax deposit in pipes

Wax deposit properties are a significant concern in pipeline pigging during waxy crude oil transportation. In the present work, the impacts of flow conditions and oil properties on the wax precipitation characteristics of wax deposits are investigated. A flow loop apparatus was developed to conduct wax deposition experiments using four crude oils collected from different field pipes. The differential scanning calorimetry (DSC) technique was employed to observe the wax precipitation characteristics of crude oil and wax deposit. The results show that the wax content and the wax appearance temperature (WAT) of the deposits increase with shear stress and radial temperature gradient, and decrease with radial wax molecule concentration gradient near the pipe wall. The DSC tests on the wax deposits revealed that the deposit wax content is strongly correlated to the oil wax content. Furthermore, an empirical correlation was developed to predict the wax content and the WAT of the wax deposit. Verification of the empirical correlation using the different oils indicated that the average relative error of the wax content prediction and average absolute error of WAT prediction were 13.2% and 3.6°C, respectively.     

Investigation of wax deposit ‘sloughing’ from paraffinic mixtures in pipe flow

Deposit ‘sloughing’ from ‘waxy’ crude oils has been described in the literature as a possible mechanism, leading to partial or complete dislodging of the deposit from the pipe wall due to changes in flow parameters. A bench‐scale flow loop apparatus was used to investigate ‘sloughing’ with prepared single‐phase ‘waxy’ mixtures of a multicomponent paraffinic wax dissolved in a multicomponent solvent. Experiments were performed to study the changes in the deposit‐layer thickness due to step increments in the ‘waxy’ mixture flow rate, the mixture temperature, and the coolant temperature. It was observed that the deposit‐layer thickness decreased with an increase in each of the three parameters; however, a complete or sudden dislodging of the deposit‐layer did not occur in any of the experiments. A steady‐state heat‐transfer model was used to predict the variation in the deposit mass or thickness due to changes in the selected parameters. In each case, the step‐wise decrease in the deposit thickness, as observed experimentally, was predicted to be caused by changes in the thermal resistance and/or thermal driving force.     

A fundamental wax deposition model for water‐in‐oil dispersed flows in subsea pipelines

Water‐in‐oil dispersions frequently form in subsea oil pipeline transportation and their presence affects the wax deposition rate in subsea pipelines. A fundamental model for wax deposition on the wall of water‐in‐oil dispersed phase flow pipelines has not been developed. Dispersed water droplets can affect the heat and mass transfer characteristics of wax deposition and alter the deposit growth rate. In this study, wax deposition from water‐in‐oil dispersed flows is comprehensively modeled using first principles of heat and mass transfer. The role of the dispersed water phase on the heat and mass transfer aspects of wax deposition is analyzed. The developed model predicts different effects of the water volume fraction and droplet size on the wax deposition rates in laboratory flow loop experiments and in field scale wax deposition processes. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4201–4213, 2017     

A review of heat-transfer mechanism for solid deposition from “waxy” or paraffinic mixtures

Summarized in this review are a large number of experimental and modelling studies for advancing the heat-transfer-based mechanism for solid deposition from “waxy” or paraffinic oils and mixtures. This comprehensive heat-transfer approach is entirely different from a more popular molecular-diffusion mechanism. It has evolved from numerous publications, over three decades, which explored topics related to thermodynamic, rheological, crystallization, solid deposition, and shutdown and deposit-aging behaviour of prepared multicomponent paraffinic mixtures of varying compositions to simulate “waxy” crude oils. These investigations covered a wide range of compositions, temperatures, and cooling rates—under static, sheared, laminar and turbulent conditions—in both the hot and cold flow regimes. The heat-transfer mechanism for wax deposition is based on (partial) freezing or liquid-to-solid phase transformation process, for which steady-state and unsteady-state mathematical models have been developed and validated with extensive laboratory data. Furthermore, a shear-induced deformation model for the deposit aging phenomenon has been developed and validated; it is based on a partial release of the liquid phase from the incipient gel, thereby causing an enrichment of heavier alkanes and a corresponding depletion of lighter alkanes in the deposit. A successful analogy with the ice deposition process has confirmed the wax deposition process to be also controlled by heat transfer, without involving any other mechanism for wax deposition. All of these previous studies confirm that wax deposition is predominantly a thermally driven process.     

Wax deposition modeling of oil/water stratified channel flow

Wax deposition modeling becomes complicated when multiphase flow is involved. Empirical heat and mass transfer correlations are unreliable for multiphase deposition modeling and full scale computational fluid dynamics calculations require expensive computational intensity. In this work, numerical methods are used to study wax deposition in oil/water stratified flow through a channel. A unidirectional flow analysis is used to calculate the nonisothermal hydrodynamics and mass transfer. It was found that the change in the position of the oil/water interface throughout the channel must be taken into accounted for the mass balance to be valid. Unfortunately, this change has not been accounted for in all previous studies. In addition, the growth of the wax deposit as a function of time along with the effect of oil/water flow rate ratio is discussed. The presence of water significantly reduces the severity of wax deposition by altering the heat and mass transfer characteristics. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Investigation of inhibitors efficacy in wax deposition mitigation using a laboratory scale flow loop

Statistically reliable wax inhibition experimental data was obtained by utilizing the newly built laboratory scale flow loop. The comb‐shaped inhibitors are found more effective in decreasing the thickness compared to the linear inhibitor under the same conditions. Moreover, this becomes more predominant as the chain length of inhibitors increases. Interestingly, even though all the inhibitors decreased the deposit thickness, the wax content increased significantly. Besides, the longer chain length (PI‐B) of the inhibitor results in a higher wax content. Since the combination of growth and aging influenced by the presence of inhibitor significantly, paraffin inhibition efficiency (PIE) based on the wax mass was proposed to quantitatively assess the inhibitors. Based on the PIE, PI‐B, and PI‐C have more inhibition efficiency than PI‐A. Therefore, when selecting wax inhibitor, one should be aware about the strength of the deposit gel in addition to the reduction of the deposit mass. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4131–4139, 2016     

聚丙烯酸十八酯降凝剂对合成蜡油结蜡特性影响的研究

采用自主研发的Couette结蜡装置研究了聚丙烯酸十八酯（POA）降凝剂对合成蜡油体系结蜡特性的影响。通过对结蜡层表面样（远离结蜡筒）和底部样（靠近结蜡筒）的宏观观察、DSC放热、气相色谱及蜡晶微观结构的分析发现：POA的加入降低了蜡油体系的结蜡速率,加快了蜡油体系的老化速率,且在一定浓度范围内（50～200 μg·g^-1）导致了径向不均质蜡沉积结构的形成,从结蜡层表面到底部含蜡量逐渐升高,但在较高加剂浓度（400 μg·g^-1）时径向不均质蜡沉积结构消失;POA的加入使得结蜡层表面样和底部样的临界碳数（CCN）都由C₂₄升高到C₂₅,但结蜡层底部样与表面样相比低碳数正构烷烃（≤ C₂₅）有所减少,高碳数正构烷烃（≥ C₂₆）有所增加;随着油样中POA浓度的增大,结蜡层表面样与底部样的蜡晶形貌由针状蜡晶逐渐转变为片状蜡晶,且蜡晶尺寸逐渐变大,结构更为致密。     

Investigating the gelling behaviour of ‘waxy' paraffinic mixtures during flow shutdown

The flow of waxy or paraffinic crude oils in a pipeline could be shutdown for a variety of reasons, resulting in their cooling and subsequent gelling. Gel formation from a multicomponent wax-solvent mixture during flow shutdown was investigated experimentally and analyzed with a transient heat-transfer model based on the moving boundary problem formulation. The gelling experiments were performed with a 0.10 g/g wax-solvent mixture in a flow-loop apparatus, following the formation of a steady-state deposit layer in turbulent flow regime, at two initial wax-solvent mixture temperatures, with a constant coolant temperature, and for different shutdown times. The gel formation was found to be a fast process, which continued until the gel fully occupied the deposition tube. Gas chromatographic analyses of the deposit samples (under sheared cooling) and the gel samples (under static cooling during flow shutdown) indicated significant differences in the composition and the total wax content. The deposit samples showed an enrichment of heavier paraffins, whereas the composition of gel samples was comparable to that of the original wax-solvent mixture. The predictions from the transient model showed that a lower initial oil temperature, a lower coolant temperature, and a smaller pipe diameter would result in a faster blockage of the pipe. The predictions from the moving boundary problem formulation agreed well with the flow shutdown data, which further confirmed that the solid and gel formation from wax-solvent mixtures is modelled satisfactorily as a heat transfer process.     

Characterization of the wax precipitation in Mexican crude oils

This paper reports the rheological and thermodynamic characterization of the wax formation phenomenon in three Mexican crude oils where the effect of waxes and asphaltenes content on wax precipitation and rheological behavior of crude oils is evaluated and discussed. Wax appearance temperature is measured by using differential scanning calorimetry, rheometry and densitometry. The wax precipitation curves were obtained by fourier transform infrared spectroscopy. Pour point temperatures were evaluated according to the ASTM-D97 method, whereas gelation temperatures were determined by rheological experiments made with a controlled-stress rheometer. Waxes of the crude oils were separated and characterized by gas chromatography/mass spectrometry and differential scanning calorimetry. The methods used in this work for the wax appearance temperature determination showed to be sensitive to the crude oil composition. Results showed that the presence of asphaltenes impacts significantly the liquid–solid equilibrium and rheological behavior of the crude oils studied whereas the wax melting temperature was a key factor to evaluate the propensity of crude oils to present wax precipitation problems.     

Wax composition of sunflower seed oils

Waxes are natural components of sunflower oils, consisting mainly of esters of FA with fatty alcohols, that are partially removed in the winterization process during oil refining. The wax composition of sunflower seed as well as the influence of processing on the oil wax concentration was studied using capillary GLC. Sunflower oils obtained by solvent extraction from whole seed, dehulled seed, and seed hulls were analyzed and compared with commercial crude and refined oils. The main components of crude sunflower oil waxes were esters having carbon atom numbers between 36 and 48, with a high concentration in the C₄₀−C₄₂ fraction. Extracted oils showed higher concentrations of waxes than those obtained by pressing, especially in the higher M.W. fraction, but the wax content was not affected significantly by water degumming. The hull contribution to the sunflower oil wax content was higher than 40 wt%, resulting in 75 wt % in the crystallized fraction. The oil wax content could be reduced appreciably by hexane washing or partial dehulling of the seed. Waxes in dewaxed and refined sunflower oils were mainly constituted by esters containing fewer than 42 carbon atoms, indicating that these were mostly soluble and remained in the oil after processing.     

含蜡原油管道结蜡厚度的计算

在含蜡原油管道的日常运行管理中,结蜡厚度是个重要参数。经常根据这个参数评价管道内部的结蜡情况．借此进行工况分析或者调整管道的运行参数。为此．建立了含蜡原油管道结蜡厚度的计算模型,并给出了相应的求解方法。求解方法快捷准确．且有较好的扩展性,结果满足工程要求。     

沥青质引发的蜡油体系结蜡层分层现象及分层规律

利用自主研发的Couette结蜡装置,对蜡含量相同的油样1(不含沥青质)和油样2[含0.75%(质量分数)沥青质]进行结蜡实验,并研究其结蜡层的分层现象和分层规律。通过对油样1和油样2结蜡表层和底层的宏观形貌、DSC放热、析蜡量、蜡晶微观形貌的分析发现:油样1结蜡层无明显分层现象,而油样2结蜡层分层现象明显,沥青质的加入导致了结蜡层的分层。与结蜡表层相比,油样2结蜡底层的析蜡点、蜡含量与沥青质含量显著升高,蜡晶形貌发展为致密的类球状大蜡晶。油样2结蜡表层沉积量随壁温的升高、油壁温差和转速的增大而减小;结蜡底层沉积量随壁温升高而减小,随油壁温差和转速的增大而增大;总的蜡沉积量随壁温的升高和转速的增大而减小,随油壁温差的增大先增大后减小。     

Mass transfer simulation on pervaporation dehydration of ethanol through hollow fiber NaA zeolite membranes

A multi‐layer series‐resistance mass transfer model was developed to simulate mass transfer behaviors of water/ethanol mixture through hollow fiber NaA zeolite membranes. The mass transfer through zeolite layer was described by Maxwell‐Stefan mechanism based on adsorption and diffusion parameters obtained from molecular simulation. The mass transfer through asymmetric hollow fiber support was described by dusty gas model involving Knudsen diffusion and viscous flow. It was found that the sponge‐like layer of support besides of zeolite layer made an important contribution to overall membrane transfer resistance while the finger‐like layer had less effect. When permeate pressure shifted from 0.2 to 7.5 kPa, the mass transfer resistance contribution of sponge‐like layer varied from 27.1 to 17.8%. Effects of microstructure parameters of support on mass transfer through membrane were investigated extensively. Large pore size and thin thickness for sponge‐like layer of support were beneficial to improve water permeation flux. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2468–2478, 2016     

蜡沉积物对现场管道运行影响研究

蜡沉积是流动保障关键问题之一,前人主要研究了温度、流速等因素对沉积物厚度的影响,而关于蜡沉积物进入原油后,对管道运行影响研究报道较少。通过现场测试储罐内原油和管输原油物性,研究了储罐蜡沉积物和管道蜡沉积物进入原油后,对管道运行的影响。研究表明:加热输送含有蜡沉积物的原油,导致原油凝点显著升高,给管道安全运行带来潜在风险,应慎用加热输送方式;升高输油温度,使管道内较松软的蜡沉积物融化,蜡沉积物厚度减小,但由于蜡沉积物进入原油,导致原油凝点升高。     

蜡沉积厚度随时间变化规律的模型研究

在分析蜡沉积过程的基础上, 基于一定的假设条件, 建立了蜡沉积厚度随时间变化的模型。通过提取蜡沉积厚度随时间变化曲线的数据, 拟合了模型中的待求常数, 并对模型计算值和实验值的吻合程度进行了分析。结果表明:对数模型、指数模型及动平衡模型均能反映蜡沉积厚度随时间的变化趋势, 对数模型与实验值的吻合程度最好;指数模型和动平衡模型所得的结果与实验结果的吻合程度相当, 在沉积初期, 指数模型的吻合程度高于动平衡模型, 但当沉积时间接近实验规定时间时, 动平衡模型的吻合程度高于指数模型;所建立的模型简单实用, 能够反映沉积厚度随时间变化的增长快慢趋势, 不同实验数据应用时仍需对各模型的计算精度进一步验证, 从而使得选用模型能更好地符合实际。     

管道结蜡层温度分布计算研究

通过对试验环道上测试段相关数据的测试,对比分析测试段管壁有沉积物和无沉积物时测试段管壁内温度分布的不同表达式,根据能量方程建立了无量纲温度分布方程,利用贝赛尔函数推导出原油在层流状态下沉积层表面温度分布、沉积层热流密度、油流温度分布等相关温度场的计算公式,为研究蜡沉积规律,定性分析管路结蜡层厚度和制定合理的清管方案奠定了理论基础.