热采用防乳破乳剂的研究与应用

稠油在热采高温作用下,容易在油层中发生乳化行为,形成稳定的油包水乳状液,给地面产出液处理流程造成一定的负担。通过分析热采放喷后产出液的含水率为28%、脱水原油的黏度为2 300 mPa·s、胶质与沥青质含量和为24.33%,从醇类、酚醛树脂类、多烯多胺类、复配类的防乳破乳剂中优选出防乳破乳剂PEC-12,幵分析了破乳温度、防乳破乳剂浓度、乳状液含水率对PEC-12防乳破乳剂破乳效果的影响。结果表明,随着破乳温度从50℃升高至80℃,防乳破乳剂的破乳率从44.6%逐渐升至98.2%。防乳破乳剂最经济有效的浓度为200ppm。乳状液中含水率从20%增至40%时,防乳破乳剂的脱水率从62.5%增至93.8%。矿场试验表明,在注热过程中添加防乳破乳剂是一种能有效抑制稠油反相乳化的有效措施,添加PEC-12防乳破乳剂后,地面处理流程显示油包水乳状液总量降低80%,稠油乳状液破乳效果好,处理负担明显减轻,同时跟地面产出液破乳剂发生了协同破乳作用,使处理后的污水中含油量达到设计要求,满足回注地层的水质要求。     

含油污泥多相复合调质降黏破乳分离过程

含油污泥普遍存在于石油开采、加工及使用等过程中，因其高黏度、复杂稳定乳化特性导致处理难度大，处理效率低。针对传统工艺分离效率低的问题，本文基于工程应用的目标，提出油泥多相复合调质降黏破乳分离工艺，对油泥进行资源化分离。首先，对含油污泥进行了不同的降黏处理，分别通过添加正庚烷和水多相复合调质的方法，可以调控体系乳化状态，溶解重质组分，破坏其空间结构，有效降低含油污泥表观黏度。在此基础上，将调质降黏与破乳相耦合对含油污泥进行资源化回收处理，分别探究了调质过程和破乳过程对处理效果的影响。结果表明，加入水辅助调质降黏，可有效分散含油污泥团聚体，促进重油溶解与传质，正庚烷通过稀释降低油组分黏度，并从固体表面溶解剥离。通过对油泥乳化态的调控，协同使用高效破乳剂可实现油、水、固的高效分离。当溶剂用量130%，水用量30%时，体系为油包水状态，添加400mg/kg油包水型破乳剂TJU-3处理后，重油回收率可达92.86%，油相清洁。本研究可以为含油污泥大规模资源化回收处理提供参考。     

用黏度法确定原油乳状液的合适破乳温度

使用旋转黏度计考察了油包水(W/O)型原油乳状液体系与原油乳状液加入破乳剂后的体系两者在表观黏度上的差别。分析了产生这些差别的原因,对其中出现的特殊现象给出了合理的解释。通过对比发现2种体系的黏度差值与适宜破乳温度存在一定的关系,并通过实验进一步验证了这种关系,为原油生产中确定适宜破乳温度提供了新途径。     

聚醚多元醇的酯化优化

用三氟乙酸和硼酸改性聚醚多元醇型破乳剂,对部分产品的黏度进行了测试,并以油包水乳化原油(w/o)破乳脱水试验为探针试验,考察改性后破乳剂的实用性.     

二元聚合物的合成及在稠油W/O乳液中的应用

采用丙烯酸(AA)与自制丙烯酸壬基酚聚氧乙烯聚氧丙烯酯(NPEAA)为原料、偶氮二异丁腈(AIBN)为引发剂、甲苯为溶剂制备了二元聚合物稠油破乳剂.采用FTIR、1HNMR对产物结构进行了确证,GPC测试了产物相对分子质量;采用荧光光谱仪与表面张力仪测得其临界胶束浓度(CMC)为0.5 g/L,表面张力为25.684 mN/m.并以脱水率和脱出污水含油量为衡量指标,探讨了不同因素下聚合物破乳剂对陈庄稠油W/O乳液的破乳脱水性能.最佳破乳条件为:温度55℃、时间2.0 h、破乳剂用量0.5 g/L,在此条件下,脱水率为88.5％,脱出水中含油量为198.4 mg/L.研究了聚合物破乳剂对乳状液表观黏度、体系稳定性、油水界面的影响以及微观破乳过程,分析得出聚合物破乳剂在油水界面处易溶解扩散,脱水速率快,破乳效果好.     

海上某油田破乳剂评选及油品性质测试研究

本文针对南海某海上油田下舱油BSW%偏高,且油田进行增产和减水增输作业的问题,在室内对破乳剂进行了破乳剂评选研究;主要考察了破乳剂的类型,加注浓度,油样含水率对脱水性能的影响;另外,测试了油样不同含水率时,黏度与温度的变化关系。结果显示:破乳剂YH-106具有更快的脱水速率和更高的终脱水量,其最佳加注浓度为80mg/L,原油含水率为20%～60%时,破乳脱水均较彻底;粘度测试结果显示:在相同含水率时,黏度随温度升高而降低;在相同温度时,黏度随含水率升高而升高,其中,在温度80℃,含水率60%时,黏度为204.2 mPa·s,所得数据对现场生产具有指导意义。     

破乳剂对聚表驱原油乳液破乳及界面膜强度关联性研究

随着驱油剂石油磺酸盐及部分水解聚丙烯酰胺(HPAM)的使用,乳化原油黏度升高、界面膜强度增大,严重影响采出液的破乳效果。对7类不同分子结构的破乳剂,从其对聚表二元复合驱O/W型原油乳液破乳效果、脱出水乳化油程度、油水界面膜强度3项进行评价,分析3项相关性和破乳剂作用效果的规律。实验表明多数破乳剂3项相关性不好,破乳剂SP169的分子结构与石蜡基原油组分相似,这是保证破乳效果好的最关键因素。     

二元聚合物的合成及在稠油破乳中的应用

采用丙烯酸（AA）与自制丙烯酸壬基酚聚醚酯（NPEAA）为原料,在偶氮二异丁腈（AIBN）为引发剂,甲苯为溶剂的条件下,引发聚合制备了二元共聚物稠油破乳剂,采用FTIR、1HNMR对产物结构进行了确证,GPC测试了分子量;采用荧光光谱仪与表面张力仪测得其临界胶束浓度(CMC)为0.5g/L,表面张力为25.684mN/m。并以脱水率和脱出污水含油量为衡量指标,探讨了不同因素下聚合物破乳剂对陈庄稠油W/O乳液的破乳脱水性能,确定最佳破乳条件：温度55?C,时间2h,用量0.5g/L时,脱水率为88.5%,脱出水中含油量为198.4mg/L。研究了聚合物破乳剂对乳状液表观粘度、体系稳定性、油水界面的影响以及微观破乳过程,探讨分析得出聚合物破乳剂在油水界面更易润湿扩散,脱水速率快,破乳效果好。     

用于复杂原油乳液的高效破乳剂开发及应用研究进展

石油生产中通常产生大量W/O、O/W或多重乳化的复杂原油乳液，造成生产效率大大降低以及严重的环境问题。目前所使用的破乳剂破乳效率低、普适性差、成本高、安全性不够等，开发高效、普适、绿色、安全破乳剂仍备受关注。本文基于原油乳液的特点及稳定机制分析，综述了不同原油乳液的破乳剂研究进展，主要围绕聚合物破乳剂、生物质基破乳剂、离子液体破乳剂和纳米材料破乳剂的特点、适用范围及其应用效果进行全面总结，对相应破乳剂的破乳机理进行针对性地分析研究，并指出破乳剂机理的研究方法。最后，本文对复杂原油乳液的高效破乳剂开发进行展望，提出破乳技术的未来发展趋势，以期为W/O、O/W或多重乳化的复杂原油乳液的破乳技术应用提供一定借鉴与参考。     

分子氧化及光电催化氧化对石油Pickering乳液的破乳研究进展

石油开采、集输、加工过程中会面临复杂的工况条件,原油中的天然表面活性剂与人工添加乳化剂以及纳微米固体颗粒共同形成石油Pickering乳液,使得油水体系呈稳定的水包油（O/W）、油包水（W/O）或多重乳化状态。油水乳状液作为注水采油的主要产物,其高效破乳是石油工业链条中的普遍需求。目前对于石油Pickering的破乳仍然借鉴普通油水乳液的方法,而对于成因复杂的油水乳状液,以去除成膜乳化剂为目标的氧化破乳法比传统破乳法的效果更佳。为此,本文基于高效的氧化破乳机制,介绍了石油Pickering乳液的特点及危害,与非氧化反应类型的传统化学破乳法进行对比,综述了分子氧化、光催化氧化、电化学氧化三类技术对于不同来源及特征的油水乳状液的破乳进展。通过对每种方法的机理过程、应用实例、优缺点等方面详细分析,总结了分子氧化、光催化氧化、电化学氧化在石油Pickering乳液破乳中的局限性,并对今后如何实现石油Pickering乳液精准破乳提出展望。     

百重七含泥沙原油破乳脱水研究

克拉玛依油田百重七稠油处理站原油乳状液中含有大量泥砂,泥沙体积含量0.6‰～1‰,给原油脱水造成困难。本文以百重七原油处理站所处理的综合原油为研究对象,研制出破乳脱水用的KXDS破乳剂;同时考察了影响原油破乳脱水的几个因素,确定出最佳破乳温度和破乳剂最佳加量。KXDS破乳剂应用于现场后,破乳剂用量由120 mg/kg降低到80 mg/kg,破乳脱水温度由85℃降低到65℃,脱后原油达到外输优质标准,污水水质达标。     

古城油田稠油脱水破乳剂的优选

以古城油田稠油乳状液为研究对象,针对稠油脱水处理问题,通过稠油高效破乳剂的室内筛选试验研究,减少稠油药剂投加量及满足含水、水质要求。测定了7种破乳剂对含水20%稠油的脱水效果,破乳剂Z61和A-20的脱水效果均优于其他破乳剂。随后进行了低温稠油破乳剂试验,对破乳剂进行了精选,同时开展了投加温度对破乳效果影响的研究试验。通过试验和分析得出,Z61优于A-20药剂;结合单个站点的试验情况,建议净水药剂的投加浓度为50 mg/L,具体的增减视分离器出水和2 000 m~3污水缓冲罐进口水质而定。     

几种采油助剂对克拉玛依油田六东区原油的影响及破乳剂筛选

针对克拉玛依油田六区稠油,在温度55℃,破乳剂加量70m g/L条件下考察了一些采油助剂对破乳脱水的影响。在低pH值区(0～8),pH值越低破乳脱水越困难,酸化返排液携带的黏土颗粒和酸液添加剂也对破乳脱水有不利影响;降粘剂浓度越大,破乳剂脱水越困难。研制出的KXDH破乳剂,应用于现场,解决了在油井大量施加采油助剂时,六东区原油脱水难,污水含油高的难题。     

Functions of Demulsifiers in the Petroleum Industry

There are an increasing number of crude oil fields that are now producing both crude oil and water emulsions; such fields are both onshore and offshore. These emulsions are formed during oil exploitation due to the presence of natural surfactants, such as asphaltenes and resins. These molecules strongly stabilize the water/oil interface and prevent coalescence of water droplets. As water/oil phase separation is necessary before oil transportation and refining, demulsifiers are used to break water-in-oil emulsions. This review presents the crude oil emulsion formation, factors affecting demulsification of crude oil emulsion such as demulsifier chemical structure, water content, partition coefficient (K_P), and demulsifier concentration. This review also covers the kinetics and mechanism of the demulsification process.     

Paraffin Oil Emulsions for the Absorption of Toluene Gas

Water‐in‐oil‐in‐water (W/O/W) and water‐in‐oil (W/O) emulsions of paraffin oil were prepared with sorbitan monooleate (Span 80)/polyoxyethylene sorbitan monooleate (Tween 80) or polyethylene glycol monostearate (SG‐6), respectively. The physical characteristics and the absorption of toluene gas in these emulsions were investigated to evaluate the influence of the emulsifier dosage and the oil/water ratio. Both investigated W/O/W emulsions provided high stabilities and low viscosities. The absorption of toluene gas was excellent, with little foam occurring during the absorption. Although the W/O emulsions with 2–5 % SG‐6 were of high stability, their high viscosities strongly limited their application as volatile organic compound absorbents. Stable emulsions consisted of small and uniform droplets and some emulsions underwent mild demulsification after the absorption.     

MPEG grafted quaternized carboxymethyl chitosan for demulsification of crude oil emulsions

Four novel environmentally friendly and highly branched crude oil demulsifiers were prepared by using different molecular weight (M_n = 350, 750, 1000, 1900 g/mol) of methoxy poly(ethylene glycol) to modify quaternized N,O‐carboxymethyl chitosan. Fourier transform infrared and ¹H‐nuclear magnetic resonance were employed to confirm the structure of the demulsifiers. The surface tension of demulsifies was determined and hydrophile–lipophile balance value was calculated at the critical micelle concentration. The demulsification performance was evaluated by the bottle test method against water‐in‐oil emulsions simulated in the laboratory and it was found that the dehydration rate of four demulsifiers can come to 74.2%–80.4%, which have better demulsification performance than the commercial demulsifier JL‐1. Demulsification mechanism was discussed, and it was encouraging to find that the tiny water droplets in the emulsion coalesced to form the water phase and separated with the water from the polarization microscope. Results show that methoxy poly(ethylene glycol) grafted quaternized carboxymethyl chitosan has a promising application as a demulsifiers for dealing with W/O crude oil emulsions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45867.     

Pipeline Flow Behavior of Water‐in‐Oil Emulsions with and without a Polymeric Additive in the Aqueous Phase

New experimental results are presented on the pipeline flow behavior of water‐in‐oil (W/O) emulsions with and without a polymeric additive in the aqueous phase. The emulsions were prepared from three different oils of different viscosities (2.5 mPa s for EDM‐244, 6 mPa s for EDM‐Monarch, and 5.4 mPa s for Shell Pella, at 25 °C). The W/O emulsions prepared from EDM‐244 and EDM‐Monarch oils (without any polymeric additive in the dispersed aqueous phase) exhibited drag reduction behavior in turbulent flow. The turbulent friction factor data of the emulsions fell well below the Blasius equation. The W/O emulsions prepared from EDM‐244 oil exhibited stronger drag reduction as compared with the EDM‐Monarch oil. The W/O emulsions prepared from Shell Pella oil exhibited negligible drag reduction in turbulent flow and their friction factor data followed the Blasius equation. The Shell Pella emulsions were more stable than the EDM‐244 and EDM‐Monarch emulsions. When left unstirred, the EDM‐244 and EDM‐Monarch emulsions quickly coalesced into separate oil and water phases whereas the Shell Pella emulsions took a significantly longer time to phase separate. The Shell Pella oil emulsions were also milkier than the EDM emulsions. The addition of a polymer to the dispersed aqueous phase of the W/O emulsions had a significant effect on the turbulent drag reduction behavior.     

表面活性剂体系改善高含蜡稠油破乳脱水效果

筛选出效果较好的几种破乳剂,与自主研制的破乳剂DH进行复配,得到DH-fp破乳剂体系,无论是室内还是现场应用,均取得良好的破乳脱水效果,达到外输油含水率低于O．5％和脱出污水含油率低于50mg·L-1。的标准。采用稳定性分析法与传统瓶试法对破乳效果进行评价,新方法与旧方法的结果一致,但可以较大地提高工作效率。     

陇东油田低温高效破乳剂的研制与应用

针对陇东油田每年夏季停炉后的低温环境（26-30℃）下,原油脱水效果不佳的问题,研制开发出了新型低温高效破乳剂。该破乳剂通过合成10种不同的破乳剂单剂,进行筛选、改性、复配得到。室内评价表明,该破乳剂在26℃下,加药量为120m g/L时,原油脱水率能达到90%;在30℃下,加药量为100mg/L时,原油脱水率能达到90%,并且脱水启动速度快,油水界面清楚,在陇东油田现场应用后,能满足现场使用要求,解决了陇东油田夏季低温破乳问题。