Slurries and emulsions of waxy and heavy crude oils for pipeline transportation of crude oil

The high viscosity of many asphaltic crude oils and the high pour points of many waxy crude oils present significant problems in their transportation over long distances by pipeline and tanker. While heating the oils and insulating the pipelines will help alleviate the problem, there is danger associated with an extended shutdown of flow and either congealing or solidification of the oil. A possible solution which we have studied in the laboratory is the emulsification or dispersion of the oil in water or brine so that shear takes place in the continuous aqueous phase rather than the oil droplets or particles.Synthetic waxy crude oils were prepared by dissolving paraffin wax in white mineral oil at slightly elevated temperatures and then measuring the pour point. One containing 30% wax had a pour point of 43°C and was selected for preparations of the dispersions. This was emulsified in water at a temperature higher than the pour point by using a suitable surfactant as an emulsifying agent. Rheological properties were measured at various temperatures and are reported in the paper. The method shows great promise for use in countries such as China which produce significant quantities of waxy crude oil and have seasonal temperatures significantly lower than the pour point of the crude oil.     

含蜡原油降凝剂与石蜡作用机理的研究进展与探讨

高分子降凝剂产品已广泛应用于原油的开采和输送工艺中,但是,对降凝剂降凝机理认识的不足制约了降凝剂的开发和应用.降凝剂与油品中石蜡的相互作用决定其降凝机理.本文综述了近年来人们在研究降凝剂与石蜡作用机理方面所使用的研究方法和所取得的进展,并深入探讨了降凝剂与石蜡的具体作用方式.对于含蜡原油,降凝剂主要通过与石蜡的共晶、吸附作用使蜡晶结构更紧凑,并促进小蜡晶聚集成较大尺寸的聚集体,从而大大降低蜡.油界面积,破坏蜡晶三维网络的形成,宏观上表现为原油凝点降低,低温流动性改善.     

含芳香基团的梳状聚合物型降凝剂与沥青质协同改善合成蜡油的流变性

采用流变学实验、 差示扫描量热(DSC)分析、 显微观察及沥青质沉淀实验研究了聚丙烯酸十八酯-马来酸酐(POM)、 聚丙烯酸十八酯-马来酸酐-苯胺(POMA)及聚丙烯酸十八酯-马来酸酐-萘胺(POMN)梳状聚合物对合成蜡油的流变性能的影响规律. 实验结果表明, 这3种梳状聚合物降凝剂均能在一定程度上改善不含沥青质合成蜡油(MO-1)的低温流变性, 其中POM对MO-1蜡油的流变性改善效果最佳. 添加500 mg/kg POM后, MO-1的凝点从29 ℃降至23 ℃, 屈服值从627.20 Pa降至83.35 Pa. 而POM, POMA和POMN可以显著改善含0.3%(质量分数)沥青质的合成蜡油(MO-2)的低温流变性, 且添加500 mg/kg POMA后MO-2蜡油的流变改善效果最佳: 凝点降至3 ℃, 屈服值降至1.27 Pa. 可见, 本文制备的梳状聚合物降凝剂均能与沥青质协同改善MO-2蜡油的流变性, 并且向POM中引入芳香基团能进一步促进沥青质与降凝剂分子的相互作用, 进而增强梳状聚合物降凝剂与沥青质的协同作用.     

倍半硅氧烷/改性乙烯-乙酸乙烯酯共聚物复配降凝剂对蜡油倾点的影响

乙烯-乙酸乙烯酯共聚物(EVA)是原油常用的降凝剂(PPDs),但其分子结构相对比较单一,对部分油品降凝效果不佳。 为了提高EVA的降凝效果,使用硬脂酰氯与羟基化的EVA直接反应的方法制备烷基长链接枝改性EVA,并与带有烷基长链的倍半硅氧烷(SS)纳米粒子进行复配。 研究了改性EVA和SS复配降凝剂对蜡油的降凝效果和降凝机理。 结果表明:复配降凝剂为蜡提供晶核,使蜡晶变小并降低蜡的沉淀量,导致蜡油中形成的蜡晶难以搭接在一起,形成了松散的结构,当复配质量比m(EVA-g)∶m(SS-L)=1∶2时,在蜡油中的质量分数为0.1%时,蜡油倾点降低了25 ℃。     

Synergistic effect between surfactants and polyacrylates-maleicanhydride copolymers to improve the flow properties of waxy crude oil

Four copolymers were prepared by copolymerization of octadecyl acrylate with maleic anhydride abbreviated as [ODM], the resulted copolymer was reacted with octadecylalcohol [ODMSA], hexadecylamine [ODMCA], benzyl alcohol [ODMBA] and aniline [ODMAn]. Three oil-soluble surfactants were also prepared by esterification of mono, di and tri ethanolamine with oleic acid, abbreviated as [MEAO, DEAO and TEAO]. These compounds were purified and characterized by FTIR, ¹H-NMR and GPC. The prepared copolymers were evaluated individually and mixed with the oil-soluble surfactants and evaluated as flow improvers and pour point depressants for waxy crude oil. It was found that, the polymer with aromatic side chain [ODMBA] exhibited the maximum pour point depression ΔPP?=?24°C at concentration 1000?ppm, while the minimum pour point depression was obtained by [ODMCA] which pronounced ΔPP?=?15°C at 1000?ppm. Furthermore, the blend [B4] between [ODMBA] and oil-soluble surfactant [TEAO] achieved extra depression of pour point (ΔPP?=?30°C). The rheological properties of the treated and untreated crude oil with the polymeric additives were also investigated and it was found that Bingham yield value (τ_B) was decreased from 1.63?Pa at 32°C to 0.3?Pa at the same temperature and 500?ppm concentration of [ODMBA].     

降凝剂对蜡油中蜡析出与溶解影响的物理化学研究

用DSC热分析仪研究了合成蜡油的加热与冷却过程,测定了蜡油在不同蜡浓度下,添加降凝剂前后的平衡蜡溶点和析蜡点以及溶解度和饱和度,并进行了热力学分析.结果表明,含蜡油的平衡蜡溶点高于平衡析蜡点,降凝剂使平衡蜡溶点进一步升高,析蜡点进一步降低,导致含蜡油凝点较大幅度降低.在实验浓度和温度范围内,该过程符合Van′tHoff方程,降凝剂使蜡的溶解焓和溶解熵增大,析出焓和析出熵减少.降凝剂提高了蜡晶析出的临界半径,增大了成核位垒,使蜡晶析出困难.     

Wax deposition rate model for heat and mass coupling of piped waxy crude oil based on non-equilibrium thermodynamics

In this paper, wax deposition in waxy crude oil transportation process was regarded as an irreversible process. Based on the entropy production rate equations, the linear phenomenological equations for the diffusion of wax molecules were derived by using the theory and method of non-equilibrium thermodynamics and heat-mass transfer. Combined with the mass and energy conservation laws, the differential equations of heat and mass transfer in the process of pipeline transportation were established, and the molecular diffusion rate of dissolved wax was solved. On the basis of this, the mathematical model of actual wax deposition rate was established by considering the attachment process and scouring process of the wax molecules. Taking an oil pipeline in Daqing as an example, the change law and influencing factors of the wax molecular diffusion coefficient, the wax deposition rate, and the net wax deposition rate were studied by numerical simulation. The wax deposition rate test results of the laboratory loop test were compared with the theoretical calculation results in order to analyze the accuracy and the adaptability of heat and mass coupling mechanism and to provide a theoretical basis for further study of wax deposition in the process of waxy oil pipeline transportation.     

Effect of Wax Composition and Shear Force on Wax Aggregation Behavior in Crude Oil: A Molecular Dynamics Simulation Study

To explore the influence of different wax components and the shear effect exerted by the pump and pipe wall in the process of crude oil pipeline transportation on the microbehavior of wax aggregation in crude oil at low temperatures, molecular dynamics models of binary and multivariate systems of crude oil with different wax components are established in this paper. The simulation results are compared with the existing experimental results and the NIST database to verify the rationality and accuracy of the models. By using the established binary model to simulate four crude oil systems containing different wax components, it can be found that the longer the wax molecular chain, the more easily the wax molecules aggregate. The influence of temperature on the aggregation process of wax molecules with different chain lengths is also studied. The lower the temperature, the greater the difference in wax molecular aggregation degree caused by the difference in molecular chain length. Nonequilibrium molecular dynamics is used to simulate the shear process of a multivariate system of crude oil, and the micromechanisms of the shear effect on the aggregation process of wax molecules are studied. Shearing can destroy the stable structure of crude oil, resulting in the orientation and conformational transformation of wax molecules, and obtaining the region of wax molecules sensitive to temperature and shear effects, the temperatures of which are below the wax precipitation point and the shear rate of which is lower than the maximum shear rate to prevent the molecular structure from being destroyed. At the same time, the sensitivity of wax components with different chain lengths to the shear effect is studied. The research results provide theoretical guidance for ensuring the safe and economic operation of waxy crude oil production.     

Phenomenological study on heat and mass coupling mechanism of waxy crude oil pipeline transport process

Based on the phase equilibrium model of the paraffin wax precipitation in the process of oil pipeline transportation, theory and method of non-equilibrium thermodynamics were applied to obtain the linear phenomenological equations for the cross-interaction of heat and mass transfer during pipeline transport, which were derived from the irreversible entropy production rate equation. Then, the analysis of the irreversible heat flow and the mass flow were carried out, and the mathematical expressions of the phenomenological coefficient of liquid phase, the phenomenological coefficient of solid phase flow, and the heat flow phenomenological coefficient were obtained. Taking a waxy crude oil transportation pipeline in Daqing Oilfield as an example, based on the analysis of liquid–solid phase equilibrium, the irreversible linear phenomenological mechanism of heat and mass coupling in waxy crude oil pipeline transportation was analyzed in detail from three levels: phenomenological coefficients which reflect characteristic of the effect of force on flow in heat and mass transfer; thermodynamic forces which trigger heat and mass transfer; transmitted heat and mass flow density, providing a theoretical basis for the further study of the wax deposition in the process of pipeline transportation.     

降凝剂与原油组分相互作用的影响因素及降凝剂发展

概述了含蜡原油中的蜡、胶质、沥青质、轻烃等有关组分与降凝剂的相互作用特点，及其对原油改性效果的影响。并结合降凝剂的改性原理，对降凝剂的发展进行了介绍。     

Preparation and Evaluation of Some Terpolymers as Lube Oil Additives

In the present work, some polymeric additives were prepared to use as viscosity index improvers and pour point depressants for lube oil via copolymerization of hexadecylacrylate and dodecylacrylate with styrene. Structure of the prepared compounds was confirmed by infrared spectroscopy and nuclear magnetic resonance. The molecular weights of the prepared copolymers were determined by using gel permeation chromatograph. The efficiency of the prepared terpolymers as viscosity index improvers and pour point depressants for lube oil was investigation. It was found that all the prepared terpolymers are effective as viscosity index improvers and pour point depressants. The viscosity index of the prepared terpolymers increases with increasing the concentration of the additives and increases by increasing the percentage of hexadecylacrylate until 70%. The best result for viscosity index of the prepared terpolymers is when the percentage of styrene is 10%. The pour point of the prepared compound decreases with decreasing concentration of additive used.     

Submicron carbon-based hybrid nano-pour-point depressant with outstanding pour point depressant and excellent viscosity depressant

We have investigated the effective utilization potential of carbon nanomaterials in the field of pour point depressants, and reported three kind of carbon-based hybrid nano-pour-point depressants with different dimensions. In this paper, poly-α-olefins-acrylate high-carbon ester pour point depressant (PAA-18) was prepared by esterification and polymerization as the basic pour point depressant. Then, the basic pour point depressant PAA18 was modified by solvothermal method with graphene oxide (GO), carbon nanospheres (Cna) and carbon nanotubes (OCNTs). The morphology and structure of the composites were analyzed by SEM, FTIR and XRD. The results showed that PAA18 was successfully in situ polymerized on GO, Cna and OCNTs. We took the simulated oil as the experimental object, and evaluated its pour point, rheological properties and wax crystal morphology, and achieved excellent results. In the three carbon-based hybrid nano-pour-point depressants with different carbon contents, the oxidation carbon nanotubes composite pour point depressant (PAA18-1 % OCNTs) with carbon content of 1 % had the best pour point and viscosity reduction effect when the dosage was 1250 ppm, which could make the pour point of the simulated oil containing wax decrease by 16 °C. PAA18-1 % OCNTs reduced the pour point by 5 °C more than PAA18. This paper provides reference for the application of carbon nanomaterials in the field of pour point depressant.     

Effect of gemini surfactant additives on pour point depressant of crude oil

Efficiencies of cationic gemini surfactant additives in improving the pour point depressant of crude oil were investigated. The length of alkyl chain is a major factor affecting the improvement of the pour point depression. The adsorption behavior of these gemini surfactants at air/solution and oil/solution interfaces were investigated by measuring the surface tension and interfacial tension as functions of concentration. It is found that there is a good relation between surface properties especially interfacial tension of the gemini surfactants and their efficiency in depressing the pour point. Also, the surface parameters and free energies of micellization and adsorption confirm the decreasing and improving of pour point depression. Crystallization study in crude oil revealed the relationship between the structure and activity of gemini surfactant additives. It is found that the x-ray diffraction patterns of waxes with additives are remarkably different from those without additives. The mechanism of the depressants action has been suggested according the adsorption of each additive. Adsorption of the additive on the surface of the wax particles inhibits their growth and alters the crystal habits through micelle core. Pretreatment of the crude oil with pour point depressants has received the greatest acceptance due to its simplicity and economy.     

Rheological behavior and structural interpretation of waxy crude oil gels

A waxy crude oil which gels below a threshold temperature has been investigated under static and dynamic conditions, using a combination of rheological methods, optical microscopy, and DSC. Particular attention is given in this work to the influence of the mechanical history on gel strength and to describing the time-dependent rheological behavior. The gels display a strong dependence of the yield stress and moduli on the shear history, cooling rate, and stress loading rate. Of particular interest is the partial recovery of the gel structure after application of small stress or strain (much smaller than the critical values needed for flow onset) during cooling, which can be used to reduce the ultimate strength of the crude oil gel formed below the pour point. A second focus of this study is to further develop the physical interpretation of the mechanism by which wax crystallization produces gelation. Gelation of the waxy crude oil studied is suggested to be the result of the association between wax crystals, which produces an extended network structure, and it is shown that the system displays features common to attractive colloidal gels, for one of which, fumed silica (Aerosil 200) in paraffin oil, rheological data are reported. The colloidal gel model provides a simple and economical basis for explaining the response of the gelled oil to various mechanical perturbations and constitutes a fruitful basis from which to develop technologies for controlling the gelation phenomenon, as suggested by the rheological results reported.     

Comparative methods in the determination of wax content and pour points of crude oils

In this research, differential scanning calorimetry (DSC) and gas chromatography is used to determine the wax content of fourteen crude oils of different sources. Different empirical equations were applied to compare the wax content of crude oils. For the fourteen crude oil samples with the wax content ranging from 7.5 to 43.8 mass%, it was observed that the results of empirical equations were in good agreement with those determined by DSC and GC. Accordingly, a correlation between ASTM pour point and the temperature at which 2 mass% of wax has precipitated out from crude oil is developed.     

Study on the Inherent Factors Affecting the Modification Effect of EVA on Waxy Crude Oils and the Mechanism of Pour Point Depression

The Ar-Sai waxy crude oils were taken as the research objects, and the viscosity reduction rates and the condensation point reduction rates were regarded as the evaluation indexes, the impacts of components content of the crude oils and carbon number distribution of waxes on the modification effect of EVA-type pour point depressant (PPD) were analyzed by using gray correlation analysis method. The oil wax was acquired by applying the extraction and separation techniques initially, then the structures and the lattice parameters of wax crystals before and after adding the PPD were studied by polarized light microscopy observation and x-ray diffraction techniques, the mechanism of pour point depression was discussed at last. The results indicate that wax content and the low carbon number wax have significant influences on the modification effect of PPD, while the impact of high carbon number wax is relatively small. Co-crystallization is the main mechanism of pour point depression, nevertheless, the impacts of the asphaltenes, resins, solid particles, and light components of the crude oils on the modification effect of the PPD cannot be ignored.     

COMPATIBILITY STUDIES ON POLYMER/WAX AND POLYMER/RESIN-ASPHALTENE BY VISCOMETRY AND PHOTOMICROGRAPHY

The compatibility of mixtures of polymeric pour point depressants, i.e. poly(ethylene-co-vinylacetate) (EVA), poly (EVA-graft-octadecylacrylate) (EVA-g-POA ), poly (ethylene-co-octadecylacrylate) (EOA) and poly(ethylene oxide-co-propylene oxide) (EO-co-PO) withwax or resin-asphaltene from crude oil have been studied by means of dilute-solution vis-cometry. It was found that each mixture pair is incompatible, but the degrees of incompati-bility are quite different, which are in good agreement with the results from photomicrog-raphy.     

Thermal behavior and solid fraction dependent gel strength model of waxy oils

Thermal behavior of waxy oils is investigated using the techniques of thermogravimetric (TG) analysis and differential scanning calorimetry (DSC). Model waxy oils and real waxy crude oils are utilized. Decomposition temperatures of waxy oils are obtained using TG analysis. The effects of thermal history, wax content, and additive on the gelation process of waxy oils are investigated using DSC. The DSC method provides a measure of wax solubility as well as solid fraction. An integration method and a computation method are utilized to predict solid fraction. In addition, wax crystallization onset points are obtained at the cooling rates ranging from 1 to 20 °C min^?1. Similarly, wax dissolution endset points are obtained at heating rates ranging from 1 to 20 °C min^?1. Extrapolated onset and endset points yield wax precipitation temperature and wax dissolution temperature, respectively. Subsequently, wax solubility curves are obtained using thermodynamic computations. A wax precipitation temperature method and a wax dissolution temperature method combine thermodynamic phase behavior with onset/endset points to predict solid fraction. Both the wax precipitation temperature method and the wax dissolution temperature method can predict solid fraction of waxy oil samples. The wax precipitation temperature method and the wax dissolution temperature method are accurate when the temperature is close to the wax appearance temperature. A heat-integration method provides accurate values of the solid fraction at temperatures significantly below the wax appearance temperature. Therefore, integration method and wax precipitation temperature/wax dissolution temperature method are combined to predict solid fraction. The effect of solid fraction on yield stress is also investigated using differential scanning calorimetry and rheometry. Finally, a new solid fraction dependent gel strength model is obtained for shut in and restart of waxy crude oil pipelines.     

含蜡原油胶凝过程特性研究

利用RS75流变仪在小振幅振荡剪切的模式下分别研究了3种不同历史条件下含蜡原油的胶凝过程, 同时通过偏光显微镜观察了不同降温速率条件下原油中的蜡晶形貌. 结果表明, 在静态降温条件下, 降温速率越大, 原油胶凝的温度越低, 原油形成的胶凝结构越弱; 并且降温速率越大, 原油在恒温静止过程中, 结构随时间恢复的速率越大, 恢复至平衡所需时间越长, 但最终的平衡结构却越弱; 在同样的降温速率下, 原油低温胶凝结构随着降温过程中剪切作用的增强而减弱, 但当历史剪切速率超过一定数值时, 原油的胶凝结构将基本不再继续变化; 在同样的历史剪切速率下, 降温速率越大, 原油在低温(31 ℃)静止初始的储能模量越小, 但最终的平衡结构却越强.     

Styrene-Maleic Anhydride Copolymer Esters as Flow Improvers of Waxy Crude Oil

Four comb-like copolymers derived from styrene-maleic anhydride copolymer were prepared and characterized by FTIR, ¹H-NMR and elemental analysis. The molecular weight was determined using GPC and their intrinsic viscosity was measured. The prepared polymers were investigated as pour point depressants and flow improvers for waxy crude oil and it was found that, the maximum depression was obtained by the sample that has long branch chain (PPD4) from 27°C to ?3°C (ΔPP = 30°C, at 10000 ppm). While, the minimum depression was exhibited by short branch chain, PPD1 (ΔPP = 21°C) at the same conditions. The effect of these polymers on the rheology and flow properties of Qarun waxy crude oil was investigated. It was found that the Bingham yield value (τ_β) decreased from 6.0 pa.s. to 0.5 pa.s. for PPD4 at 27°C and 10,000 ppm. The dynamic viscosity also decreased from 110 m pa.s. to 24 m pa.s. for the same sample and the same conditions.