一种树状多支化破乳剂的合成与应用

为了提高渤海S油田原油乳状液的破乳效果,先采用苯乙烯和马来酸酐自由基聚合反应合成苯乙烯-马来 酸酐共聚物（SMA）,然后与1.0 代聚酰胺-胺（1.0G PAMAM）进行酰胺化接枝反应,得到以聚苯乙烯-马来酸酐共 聚物为主链、以1.0G PAMAM 为侧链的多支化水溶性破乳剂TS-Z806。考察了该破乳剂在不同温度（50～ 90 ℃）下对原油乳状液的破乳效果,并与聚醚类破乳剂JM-01 的破乳效果进行对比,采用该破乳剂首次在渤海 油田进行现场应用。室内和现场试验结果表明,温度大于70 ℃后,聚醚类破乳剂JM-01 对原油乳状液的脱水率 明显降低,脱水水质变差,故破乳效果变差;而非聚醚类破乳剂TS-Z806 在高温下对原油乳状液仍表现出良好的 破乳效果。破乳剂TS-Z806 在处理渤海S油田原油综合管汇处含聚合物采出液时,表现出了优异的破乳性能,能 够明显改善脱出水的水质,破乳后上层油乳化层较低,脱水后乳化层减少约69%。该破乳剂可实现对含聚合物 采出液的高效处理,具有较好的现场应用前景。     

改性树状大分子W-PAMAM的合成及破乳性能研究

在适宜的工艺条件下合成了支化代为0.5~2.0G的聚酰胺-胺型树枝状系列高分子（PAMAM）,并将2.0G PAMAM与环氧丙烷及环氧乙烷进行烷氧基化反应,制备了具有多分支结构的聚醚类破乳剂W-PAMAM。考察了整代PAMAM破乳剂和改性W-PAMAM破乳剂对水包油（O/W）型模拟原油乳液的破乳性能。实验结果表明,整代PAMAM破乳剂和改性W-PAMAM破乳剂均对O/W型模拟原油乳液有破乳作用,在温度为60℃、破乳时间为120 min、加量为100mg/L时,W-PAMAM对含油5%的O/W型模拟原油乳液的破乳除油率大于90%。     

聚醚破乳剂结构与压裂乳状液破乳效果的关系

以1,3-丙二醇、四乙烯五胺、聚酰胺-胺为起始剂合成了直链型、支链型及枝状聚醚破乳剂,采用瓶试法测定了这些破乳剂对模拟压裂乳状液的破乳效果,考察了破乳剂类型及分子结构对破乳效果的影响。结果表明,支链聚醚破乳剂的破乳效果优于直链聚醚破乳剂,且支化程度增加对破乳有利;以3.0代枝状聚酰胺-胺为起始剂的聚醚破乳剂破乳效果最好,当环氧乙烷与环氧丙烷的质量比(m(EO)/m(PO))为1/3、起始剂质量分数为0.5%时,制备的枝状聚醚破乳剂对模拟压裂乳状液7min即可完全破乳。     

树枝状聚酰胺-胺PAMAM的破乳性能与破乳机理

采用发散法合成了以氨和乙二胺为核心的1.0G、2.0G、3.0G树枝状聚酰胺-胺(PAMAM),简介了合成方法。加剂量为150mg/L时聚酰胺-胺对由5.0g原油、0.2gOP-7 DDBS、94.8g蒸馏水制成的高度稳定的O/W乳状液的脱水率(45℃,90min),随聚酰胺-胺代数G的增大而增大,乙二胺核心聚酰胺-胺的破乳率(98%,3.0G)高于氨核心聚酰胺-胺(91%,3.0G)。20mg/L乙二胺核心3.0G聚酰胺-胺使大庆采油一厂试验大队联合站含聚合物和碱的采出液的脱水率(45℃,90min)达到84.6%,脱出水含油68mg/L;而聚醚破乳剂SP169和BP169在加剂量为150mg/L时才能达到这一脱水率,而且脱出水含油高达356~370mg/L。用单滴法测定的油滴破裂速率常数k随聚酰胺-胺加量增大和代数G增大而增大。认为树枝状聚酰胺-胺的破乳机理与这种大分子具有球形分子结构,球形表面上含有大量极性胺基官能团有关。图1表2参7。     

对我国理想原油破乳剂的开发思路

根据原油乳状液稳定与破乳机理,认为理想的破乳剂的必备条件是:①较强的表面活性;②良好的润湿性能;③足够的絮凝能力;④较好的聚结效果。我国对理想的原油破乳剂的研究应用起步较晚,现在使用的破乳剂品牌虽多但单剂品种少,最近开发成功的破乳剂产品大多还是聚醚型。今后理想的原油破乳剂的研发目标应是:①应加大具有全新化学结构的高效破乳剂研究,逐步用非聚醚型破乳剂取代聚醚类破乳剂;②加强对三次采油技术采出的原油乳状液破乳机理的研究;③急需研制一种破乳能力强、脱后污水质量好并适应含聚合物、碱、表面活性剂的原油采出液处理的破乳剂;④适合于稠油乳状液的高效破乳剂的研制迫在眉睫。     

疏水缔合聚合物驱体系中原油乳状液性质及破乳规律

采用瓶试法考察了原油组成及疏水缔合聚合物（Hydrophobically associating polymer, HAP）质量浓度对原油乳状液稳定性的影响,用油 水界面张力、界面电性、界面扩张流变、界面剪切黏度等多个参数表征了HAP驱采出液油 水界面性质的变化规律,用一系列酚胺树脂聚醚破乳剂对模拟采出液进行破乳。结果表明,原油中胶质和沥青质是影响原油乳状液稳定的重要因素;实验浓度范围内,随着HAP浓度升高,原油乳状液稳定性增强。HAP具有界面活性,吸附在油 水界面可降低界面能,利于乳化;HAP在界面上形成交联网状结构,提升了界面膜的扩张模量和剪切模量,同时增强了界面膜的负电性,利于稳定乳状液。环氧乙烷与环氧丙烷各占一半的酚胺树脂聚醚破乳剂与1%甲苯二异氰酸酯（TDI）交联后,5 min即可完全将原油乳状液破乳。     

西峰原油化学破乳脱水特性研究

西峰油田目前属于开发初期，其含水量不高，约为10％-30％，所形成的乳状液为油包水型乳状液。对适合西峰原油乳状液破乳脱水的化学破乳剂及其处理条件进行了实验筛选。结果表明，106型原油破乳剂为最佳破乳剂，最佳破乳条件为：破乳温度40℃，加剂量40mg／L。     

哈拉哈塘油田稠油破乳剂的选取

依据中华人民共和国石油天然气行业标准筛选出适合塔里木油田哈拉哈塘油田哈6区块稠油乳状液的破乳剂,并通过脱水量、油相中含水量、油水界面等技术指标,评价破乳剂在不同条件下破乳脱水效果,优选出效果最优的破乳剂,作为哈拉哈塘油田哈6区块原油脱水的专用原油破乳剂。在室内模拟条件下,用哈拉哈塘油田稠油配制出的含水10%、30%、60%的原油乳状液为较稳定的油包水型乳状液,能够满足室内原油破乳剂的筛选试验要求。筛选出的TA209破乳剂能够满足一段破乳脱水条件要求,筛选出的JFO913破乳剂能够满足二段破乳脱水条件要求。     

原油破乳剂的胜利油田的应用和发展

本文综述了原油破乳剂在研制与应用概况，按研制时间先系统介绍了１９种原油破乳剂，包括１８种用于油包水型乳状液的破乳剂和１种用于水包油型乳状液的乳剂，提出了当前发展原油破乳剂的三个紧迫问题。     

原油破乳剂在胜利油田的应用和发展

本文综述了原油破乳剂在胜利油田研制与应用概况，按研制时间先后系统介绍了１９种原油破乳剂，包括１８种用于油包水型乳状液的破乳剂和１种用于水包油型乳状液的破乳剂，提出了当前发展原油破乳剂的三个紧迫问题。     

模拟凝析油乳液破乳剂的制备与评价

以不同物质量配比的醇类为起始剂,路易斯酸为催化剂,环氧氯丙烷作为接枝物,按照正交实验设计的条件,起始剂与环氧氯丙烷发生接枝聚合反应得到系列活性中间体;该中间体与有机胺A发生胺化反应制备凝析油破乳剂。采用单因素法对反应物配比、反应时间对破乳剂破乳性能的影响进行了优化研究,得到了较佳的工艺条件。应用室内瓶试法,对系列凝析油破乳剂的破乳性能进行了性能评价,考察了破乳剂组成对脱水效果的影响,筛选出了性能较好的破乳剂,通过复配探讨了不同凝析油破乳剂之间的协同效应,得到了性能优异的凝析油破乳剂;探讨了破乳温度与破乳剂加量对其破乳性能的影响。结果表明,最佳破乳剂在其加量为20 mg/L的情况下,便能达到很好的脱水效果,油水界面清,净水效果最好。该破乳剂,具有油水分离速度快、油水界面清和油水不易乳化等特点。最后,对最佳凝析油破乳剂的结构进行初步表征。     

An evaluation of lignocellulosic solutions from OPEFB pulping process as demulsifiers for crude oil emulsion demulsification

Lignocellulosic solutions from oil palm empty fruit bunch (OPEFB) organosolv pulping process are used as demulsifiers for demulsification of crude oil emulsion using a model of water-in-oil emulsion of crude oil and brine solution. The results indicate that the demulsification performance was favored when only lignin compound was contained in the demulsifier. The phase separation capacity and rate were strongly affected by brine pH values, temperatures and demulsifier dosages. Complete phase separation capacity was achieved at the optimum conditions. The separated oil and water are qualified for refining process and water treatment, respectively, making it promising as a demulsifier.     

Optimization of separation of oil from oil-in-water emulsion by demulsification using different demulsifiers

Separation of oil from oil-in-water emulsion is a major challenge in petroleum industries during the producing and refining process. The authors investigated characterization of oil-in-water emulsion and subsequently separation of oil from emulsion using different chemical dimulsifiers. The effect of settling time, pH, temperature, and demulsifier dosage on oil separation efficiency has been studied. It was observed that as time, temperature, and chemical dosage increased oil separation efficiency increased. Droplet size distribution of emulsions illustrated that the demulsifier could lead to the breakup of crude oil-in-water emulsions by flocculation and coalescence. More than 98% oil separations were observed with some demulsifiers under optimum operating conditions.     

电化学方法研究微生物表面活性剂对原油乳状液破乳的作用

选用一种微生物表面活性剂分别与 3种破乳剂GE 189、XE 12 0和XP 12 0复配 ,对模拟原油乳状液进行破乳脱水。结果表明 ,微生物表面活性剂的引入能够明显地提高破乳剂的破乳速率和效率 ,而且当破乳剂的浓度较低时 ,微生物表面活性剂的影响更加明显。通过界面张力的测定 ,证实了微生物表面活性剂和破乳剂之间的协同作用。利用电化学方法测定水 油 水界面的膜电容和膜电阻 ,探讨了微生物表面活性剂对原油乳状液破乳效果的影响机理。结果表明 ,单独使用微生物表面活性剂 ,观察不到膜电容和膜电阻的任何变化 ;微生物表面活性剂与破乳剂复配 ,界面膜电容随时间的升高与界面膜电阻随时间的下降幅度明显大于单独使用破乳剂时的情况 ,也表明了微生物表面活性剂与破乳剂之间的协同效应。而且由于微生物表面活性剂的加入 ,引起膜电容的迅速升高和膜电阻的迅速下降与乳状液破乳脱水速率的加快密切相关 ,说明该种电化学方法用于破乳机理的研究是可行的。     

DL32 破乳剂对船用油油水界面的影响

分析了有无破乳剂时船用油与水界面的情况，阐明了船用油易乳化的原因。加入新型破乳剂ＤＬ３２后，船用油分水性能得到明显的改善，其原因是破乳剂分子能强烈吸附于界面，而又不形成坚固的界面膜。破乳剂的这一性质对船用油乳化液的破乳也是有利的。     

聚乙二醇-聚丙烯酸丁酯共聚物的破乳作用

合成了新型油溶性破乳剂(SD-1)并对其进行了破乳实验,考察了实验温度、破乳剂加量、乳化原油的油水比等因素对破乳效果的影响,并通过破乳效果和界面张力测定与常见聚醚型破乳剂进行比较。结果表明,在50℃,油水体积比7∶3的体系,破乳剂用量小于70mg/L时,合成的破乳剂脱水效果明显好于现有的油溶性破乳剂。     

Demulsifier performance at low temperature in a low permeability reservoir

The crude oil in Longdong area is produced in the form of emulsion containing associated oil and water, which needs to be separated before dispatch to end user. Chemical demulsification under high temperature is the most widely used technology to break the emulsions. In this study a rheological method was used to determine the curve of viscosity-temperature and lower limit of temperature was determined. A series of experiments on low-temperature commercial demulsifies were implemented for studying demulsification performance by bottle test method. Mechanism of low-temperature demulsifier was studied by using spinning drop interfacial tensiometer to determine interfacial tension between the crude oil and demulsifier solution by considering the concentration. Turbiscan stability analyzer was used to study the effect of water content, temperature, and demulsifier concentration on emulsion stability. The corresponding relationship between interfacial tension and demulsification was verified through the study of low-temperature demulsifier effect on interfacial tension. Efficient low-temperature demulsifiers AR102, AR901, PR929, and PRC06 were selected. PRC06 was chosen to be the best at 40°C, and when the optimal concentration was 200 mg/L, dehydration rate was 99.51%.     

Optimum demulsifier formulations for Nigerian crude oil-water emulsions

The formation of crude emulsion during oil production and processing is a challenge of significant proportions to the oil producers. Studies show that about two third of Nigerian crude oil production is in form of water in oil emulsion. For economic and operational reasons, it is necessary to separate the water completely from the crude oil before transportation or refining.Efficiency of separation of crude emulsions is of major importance to producers. To this end, this study primarily seeks to investigate the formulation of effective demulsifier that can be used to achieve this aim; and in so doing, the optimal separation efficiency attainable by this demulsification process is determined. Six different samples of water and oil soluble demulsifiers were used on two different samples of synthetic emulsion (sample I and II (both water in oil emulsion) from different Nigerian oil fields). The bottle test method was used to determine the percentage water separation for each crude oil emulsion/chemicals (demulsifiers) mixture. The concentrations of the combined six chemicals (demulsifier samples A–F) in the mixture were related to the percentage water separation using response surface methodology central composite design (RSMCCD).Results show that the optimum concentrations of demulsifiers A–F are 59?ppm/39?ppm/29?ppm/20?ppm/29?ppm/13?ppm respectively for crude oil sample I. While 54?ppm/40?ppm/25?ppm/21?ppm/29?ppm/8?ppm respectively were observed as optimum concentration for crude oil II. The combination of these chemical was observed to return better performance than the existing commercial demulsifiers with percentage water separation of 92% and 94% compared to percentage water separation of 87% and 90% returned by one of the currently available demulsifier used in the petroleum industry for crude oil A and B respectively. Hence, the need to carry out optimization analyses on different emulsified crude oil cannot be over-emphasize.     

高分子表面活性剂驱采出液破乳剂的研制和现场试验

针对大庆油田高分子表面活性剂驱试验井的采出液,合成了系列原油破乳剂。在大庆油田采油现场对6种破乳剂进行了试验评价,研究了油基破乳剂和水基破乳剂的配伍性,探讨了加药方式对破乳效果的影响。试验结果表明：单独使用油基破乳剂或水基破乳剂皆不能达到现场生产要求;油基破乳剂YJ01与水基破乳剂具有良好的配伍性,油基破乳剂YJ02与水基破乳剂不配伍;采用先加入油基破乳剂YJ01,5min后再加入水基破乳剂SJ02的加药方式能取得良好的破乳效果,破乳后油相含水率与水相含油率皆达到现场生产指标要求。