THE INFLUENCE OF VINYL ACETATE CONTENT OF THE POLY(ETHYLENE-CO-VINYL ACETATE) (EVA) ADDITIVE ON THE VISCOSITY AND THE POUR POINT OF A BRAZILIAN CRUDE OIL

Petroleum companies have enhanced the offshore exploration, where the fields are located under deep water. In such cases, the low temperature of the water leads to the cooling of the oil and provokes wax deposition. Several techniques are used to reduce the problems caused by wax deposition. Polymeric additives, as ethylene-co-vinyl acetate co-polymers (EVA), are intensively used. In this work, the influence of the EVA vinyl acetate content on the viscosity and the pour point of a Brazilian crude oil was evaluated, and correlations for these properties as a function of the EVA co-polymer concentration were established. EVA copolymers were used containing 22,32,40 and 82 wt% of vinyl acetate and the 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 in which the wax crystals start forming the copolymer exhibited a strong influence on the oil viscosity reduction at an optimum concentration. The pour point results showed the best efficiency to EVA 32. The results obtained from both experiments showed that the viscosity and the pour point behaviors do not present good correlations to each other.     

THE INFLUENCE OF VINYL ACETATE CONTENT OF THE POLY(ETHYLENE-CO-VINYL ACETATE) (EVA) ADDITIVE ON THE VISCOSITY AND THE POUR POINT OF A BRAZILIAN CRUDE OIL

Petroleum companies have enhanced the offshore exploration, where the fields are located under deep water. In such cases, the low temperature of the water leads to the cooling of the oil and provokes wax deposition. Several techniques are used to reduce the problems caused by wax deposition. Polymeric additives, as ethylene-co-vinyl acetate co-polymers (EVA), are intensively used. In this work, the influence of the EVA vinyl acetate content on the viscosity and the pour point of a Brazilian crude oil was evaluated, and correlations for these properties as a function of the EVA co-polymer concentration were established. EVA copolymers were used containing 22,32,40 and 82 wt% of vinyl acetate and the 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 in which the wax crystals start forming the copolymer exhibited a strong influence on the oil viscosity reduction at an optimum concentration. The pour point results showed the best efficiency to EVA 32. The results obtained from both experiments showed that the viscosity and the pour point behaviors do not present good correlations to each other.     

Chemical Structure Effect of (Meth) Acrylic Ester Copolymers and Modified Poly (Etliylene-co-Vinyl Acetate) Copolymer on Paraffin Deposition Prevention in Crude Oil

Acrylic and methacrylic esters copolymers in various compositions: were synthesized in order to study the chemical structure effect over their effectiveness as pour point reducers in crude oil. Copolymerization results data from octadecyl methacrylate, hexadecyl methacrylate with methyl methacrylate and octadecyl acrylate, hexadecyl acrylate with methyl acrylate revealed superior results for acrylate monomers compared to methacrylate ones. Copolymers of ethylene and vinyl acetate (EVA) containing 19, 31 and 40% of vinyl acetate were chemically modified aiming to improve their performance as pour point reducer in crude oil. Ester pendant groups were introduced in the copolymer main chains resulting in meaningful increase of their performance as additive.     

Chemical Structure Effect of (Meth) Acrylic Ester Copolymers and Modified Poly (Etliylene-co-Vinyl Acetate) Copolymer on Paraffin Deposition Prevention in Crude Oil

ABSTRACT

Acrylic and methacrylic esters copolymers in various compositions: were synthesized in order to study the chemical structure effect over their effectiveness as pour point reducers in crude oil. Copolymerization results data from octadecyl methacrylate, hexadecyl methacrylate with methyl methacrylate and octadecyl acrylate, hexadecyl acrylate with methyl acrylate revealed superior results for acrylate monomers compared to methacrylate ones. Copolymers of ethylene and vinyl acetate (EVA) containing 19, 31 and 40% of vinyl acetate were chemically modified aiming to improve their performance as pour point reducer in crude oil. Ester pendant groups were introduced in the copolymer main chains resulting in meaningful increase of their performance as additive.     

江汉原油降凝剂的制备及其性能研究

利用溶液聚合反应合成了一系列丙烯酸酯类高蜡原油降凝剂,并对其降凝效果进行研究。研究结果表明：采用摩尔配比为6：3：1的丙烯酸十八酯,马来酸酐和醋酸乙烯酯组成的混合单体制备的三元聚合物高蜡原油降凝剂MVA-3对江汉原油具有明显的降凝效果,在加剂量为1000mg／kg时,可以使江汉原油的凝点降低12℃。高蜡原油降凝剂MVA-3能够同原油中的胶质和沥青质有效结合,可以降低原油中固有的胶质一沥青质聚集体在原油中的析出温度,改变原油中蜡的结晶方式,降低蜡结晶析出温度和蜡结晶析出速度,并能减少原油中蜡的析出总量。     

高凝原油降凝剂的制备及其降凝机理研究

 由丙烯酸十八酯、马来酸酐和醋酸乙烯酯三元共聚物的胺解改性物（MAVA）和乙烯-醋酸乙烯酯的共聚物（EVA）为原料,通过复配制备了一种高凝原油降凝剂(PPD),并对其降凝效果和降凝机理进行了研究。结果表明,所制备的高凝原油降凝剂对凝点为43℃的胜利原油具有明显的降凝效果,在加剂量为400?g/g时,原油的凝点降低了11℃;由原油中的沥青质和胶质所形成的聚集体结构是原油的蜡晶成核剂,降凝剂可以同原油中的沥青质和胶质结合形成新的沥青质-降凝剂-胶质聚集体结构,该聚集体结构作为加剂原油的蜡晶成核剂,可以改变蜡的结晶方式,延缓蜡晶的析出速率,大幅地降低了原油的凝点。     

POLY(ETHYLENE-CO-VINYL ACETATE) (EVA) COPOLYMERS AS MODIFIERS OF OIL WAX CRYSTALLIZATION

This work describes the performance of poly(ethylene-co-vinyl acetate) (EVA) copolymers as pour point reducer and organic deposits inhibitor. The molecular weight, molecular weight distribution and vinyl acetate content of the EVA copolymers were determined by gel permeation chromatography and thermogravimetric analyses, respectively. The copolymer with the highest vinyl acetate content (within the range analyzed, 28-41 wt %) exhibited the best performance as organic deposits inhibitor. Results from differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) suggest that the EVA copolymer acts modifying the morphology of the wax crystals.     

POLY(ETHYLENE-CO-VINYL ACETATE) (EVA) COPOLYMERS AS MODIFIERS OF OIL WAX CRYSTALLIZATION

ABSTRACT

This work describes the performance of poly(ethylene-co-vinyl acetate) (EVA) copolymers as pour point reducer and organic deposits inhibitor. The molecular weight, molecular weight distribution and vinyl acetate content of the EVA copolymers were determined by gel permeation chromatography and thermogravimetric analyses, respectively. The copolymer with the highest vinyl acetate content (within the range analyzed, 28-41 wt %) exhibited the best performance as organic deposits inhibitor. Results from differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) suggest that the EVA copolymer acts modifying the morphology of the wax crystals.     

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。     

高凝原油降凝剂的合成及复配性能研究

根据高凝原油组成以及降凝剂对原油的感受性确定了合成降凝剂的高碳醇的碳数,以丙烯酸和C18～C22混合醇为原料,合成丙烯酸高碳醇酯,得到三种聚合物:丙烯酸酯自聚物(AM),丙烯酸酯-醋酸乙烯酯(AMV)和丙烯酸酯-醋酸乙烯酯-苯乙烯(AVS)。比较了三种聚合物的降凝效果,选出AVS考察其合成条件并且与常用降凝剂EVA进行复配。实验结果表明:丙烯酸酯、醋酸乙烯酯、苯乙烯最佳配比为1∶1∶0.5,引发剂用量为1.2%,单体质量浓度30%,反应时间为7h时,三元共聚物AVS与EVA的复配物CPR可以使魏岗原油凝固点降低10℃,防蜡率达到40.62%。     

Aminated Copolymers as Flow Improvers for Super-viscous Crude Oils

The new flow improvers for super-viscous crude oils were developed via esterification of polybasic high carbon alcohol with methacrylate and copolymerizafion of monomers followed by amination of copolymers. The structure of the synthesized polymer flow improver additive was confirmed by IR spectroscopy and the crystal structure of the flow improver additives were determined by X-ray diffrac- tion analysis. The structure of wax crystals was also studied at the same time. The results showed that the wax crystal structure was closely related with the crystal structure of the flow improver, which could change the pour point depression and viscosity reduction behavior of the crude oil. When the wax crystal structure matched well with that of the additive, the wax crystals were dispersed satisfactorily, resulting in favorable effects in terms of pour point depression and viscosity reduction. The new synthe- sized aminated polymer flow improver additive was most efficient for treating super-viscous crude oils. The super-viscous crude oil had a high content of resins and asphaltenes, which might aggregate onto the surface of wax crystals to form blocks to limit the crude oil fluidity. However, amination of copolymers having similar structure with the resins and asphaltenes contained in crude oil could dissolve the huge polar groups to make the deposit formation difficult.     

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.     

潍北高凝点原油降凝降黏剂的研制

实验室自制的三元共聚物AMV-22与EVA复配,添加SLA-107作助剂,制备适用于胜利油田潍北区块高凝点原油的降凝剂AMVES。实验考察了该降凝剂对原油的降凝降黏效果。DSC热分析结果表明,AMVES加量为1000 mg/L时,可使原油凝点从48℃降低到37℃,析蜡点降低2℃。流变性曲线表明原油的剪切稀释作用随温度升高显著增强,当剪切速率大于100 s^-1后黏度基本不变,降凝剂可以大幅降低启动原油的屈服应力。偏光显微镜图显示原油温度越低,蜡晶网状结构越致密,交联度强,黏度大,流动性差;加AMVES之后原油中蜡晶变为团簇状颗粒,原油的流动性增强。由此可见降凝剂AMVES作用于蜡晶使其三维网状结构破坏,从而有效降低原油凝点和黏度。     

管输温度对EVA型防蜡剂防蜡效果的影响

采用Couette蜡沉积实验装置研究了聚乙烯醋酸乙烯酯(EVA)型防蜡剂对长庆原油蜡沉积特性的影响,分析了不同管输温度条件下EVA型防蜡剂的防蜡效果。研究发现,与空白原油相比,加剂原油的蜡沉积速率大幅降低,同时蜡沉积物的老化速率升高。无论是在恒定油壁温差还是在恒定壁温条件下,EVA型防蜡剂的防蜡效率均随油温的升高而不断降低,EVA对蜡沉积物老化速率的提升幅度均随油温的升高而不断增大。通过分析EVA型防蜡剂对长庆原油流动特性、低温胶凝结构特性及微观蜡晶形貌的影响,阐明了EVA型防蜡剂对长庆原油蜡沉积特性的影响机理,并从蜡沉积物初始凝油层抗剪切强度及蜡分子扩散速率2个角度揭示了管输温度对EVA型防蜡剂防蜡效果的影响。     

胺解聚合物型原油降凝剂的合成及应用

通过丙烯酸高碳酯与马来酸酐、醋酸乙烯酯、苯乙烯共聚后进行不同系列胺解得到一系列新型高蜡原油降凝剂。考察了该类降凝剂对大庆高蜡原油和尼尔阿曼混合原油的降凝效果。结果表明，胺解聚合物型原油降凝剂具有较好的原油降凝性能，降凝幅度最高达到27℃；同时，测定了加剂温度对降凝剂降凝效果的影响，结果发现，当加剂温度高于原油析蜡温度时，降凝剂的降凝效果才能充分显现出来。     

Evaluation of the inhibitor selection on wax deposition for Malaysian crude oil

Wax precipitates from crude oil when a fluid is cooled down below its wax appearance temperature (WAT). This particularly happens during the transportation of crude oil in the pipeline system. In this study, chemical inhibitors were chosen to prevent and reduce wax formation using seven different types of inhibitors, which are poly (ethylene-co-vinyl acetate) (EVA), poly (maleic anhydride-alt-1-octadecene) (MA), diethanolamine (DEA), cocamide diethanolamine (C–DEA), toluene, acetone, and cyclohexane. The total waxes deposited from the cold finger test are subjected to the type of inhibitor, rotation speed of impeller, and inhibitor concentration. EVA is suggested as the most effective inhibitor based on the amount of wax deposit weight and the value of viscosity. Therefore, this result might be useful for further research work related to wax deposition in the area of crude oil production.     

超临界CO2处理对长庆原油添加降凝剂效果的影响

利用超临界CO2(scCO2)与原油混相处理装置,模拟地层条件对长庆原油进行超临界CO2混相处理,通过对处理前后油样的四组分(SARA)、沥青质稳定性、蜡析出曲线、凝点、流变性分析及微观显微观察,从沥青质缔合状态与蜡结晶层面分析了超临界CO2处理对乙烯 醋酸乙烯共聚物(EVA)降凝剂添加到长庆原油作用效果的影响。结果表明,超临界CO2处理加剂原油相比未处理加剂原油具有更好的低温流动性能。超临界CO2处理会增加未加剂原油体系极性,增强沥青质缔合程度,使低温下蜡晶形貌更细小,恶化原油低温流动性,而超临界CO2处理后添加EVA降凝剂却使得蜡晶形貌向更加紧密的团簇转化。由于超临界CO2处理有利于EVA降凝剂进一步改善蜡晶形貌,故超临界CO2处理可以促进EVA降凝剂对长庆原油低温流动性的改善效果。     

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(EV A)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EV A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...     

降凝剂对原油中蜡非等温结晶行为的影响

以乙烯-醋酸乙烯酯共聚物(EVA)和聚丙烯酸高碳醇酯(PA)为主要原料,制备了一种高凝原油降凝剂（PA-EVA）,采用差示扫描量热法研究了降凝剂的添加对原油中蜡的非等温结晶动力学的影响。结果表明：PA-EVA降凝剂起到了异相成核作用,使蜡的结晶峰温升高,结晶速率增大;PA-EVA降凝剂通过增大蜡晶几何尺寸,减少了对液态油的包覆,从而改善原油的流动性。     

固相沉积模型在高凝油藏注水开发中的应用

传统的油-水两相热采模型在进行高凝油注水开发的数值模拟过程中,仅能考虑黏度和相对渗透率曲线随温度变化的影响,而无法表征蜡的固相沉积作用对储层物性的伤害,这种物性变化也是应用不同温度下相对渗透率曲线的前提.为弥补两相热采模型中的这一缺陷,提出了利用固相沉积模型模拟高凝油藏开发,建立了油-水-固三相的热采数值模拟方法,通过与两相热采模型的模拟结果对比,表明蜡沉积对储层渗透率的伤害是高凝油田早期注水开发中最大的影响因素.同时结合热采模型获得了不同注水温度下蜡沉积半径及伤害程度等的定量认识,对更好地研究和预测高凝油田注水开发动态具有重要的指导意义.