原油破乳剂研究发展综述

综述了国内外原油破乳剂的研发情况，提出了国内今后发展途径，对国外和国内研发历史作了较详尽的叙述。将国外研发的原油破乳剂分为9大类并作了扼要介绍，国内研发的破乳剂分为10大类，分别介绍了主要结构特点和常见商品牌号，其中关于复配破乳剂则介绍了重要的应用性研究结果。关于今后发展，提出了深海，寒冷地区，稠油及化学驱油藏用的原油破乳剂，在现有知识基础上研发新破乳剂的技术路线及破乳剂复配的重要意义。     

聚甘油丙烯酸酯扩链剂合成原油破乳剂

以丙烯酸丁酯（BA）、甲基丙烯酸甲酯（MMA）和苯乙烯（ST）为原料，聚甘油丙烯酸酯为扩链剂，过氧化二苯甲酰（BPO）为引发剂，甲苯为溶剂，进行自由基聚合，合成了一种非聚醚类的原油破乳剂。考察聚合诸因素对产物破乳性能的影响。实验表明，当单体质量比（MMA：BA：ST）为1：3：1，单体总量9g，聚甘油丙烯酸酯1．3g，引发剂用量为0．2g，溶剂用量30g，聚合温度80℃，反应时间6h时，原油破乳效果最好，在破乳剂加量300mg／L时，原油破乳脱水率达72．43％。     

The Demulsification of Crude Emulsion of ASP Flooding by an Organic Silicone Demulsifier

Abstract

In order to enhance crude oil recovery, the dosages of alkali, surfactant, and polymer in the tertiary flooding are becoming increasingly higher, which makes the emulsion more difficult to demulsify. In this article the application of new organic silicone demulsifiers for the demulsification of produced crude emulsion of alkali-surfactant-polymer (ASP) flooding with higher concentrations of alkali, surfactant, and polymer was investigated. The result indicated that organic silicone demulsifiers whose hydrophile–lipophile balance (HLB) number ranged from 10 to 15 had a satisfactory effect on demulsification. The dewatering efficiency can be improved evidently by adding a demulsifier mixed with DC2 and JG31 whose volume ratio was 4:1. The dewatering efficiency for produced crude emulsion from ASP flooding could exceed 80% at 60°C in which the concentrations of alkali, polymer, and surfactant ranged from 1,200 to 9,000 mg/L, 400 to 1,000 mg/L, and 200 to 800 mg/L, respectively. The simulative industrialized experiment of the ASP flooding produced emulsion was made, the dewatering efficiency was 99.6%, and the oil content of the produced water was less than 100 mg/L.     

流花原油脱水技术参数选择

以流花原油脱水为主线,通过探究流花原油对不同低温破乳剂在储罐中不同温度、不同混合程度、不同沉降时间,摸索出油水分离清晰、罐区能耗最小的操作条件和筛选出合适的低温破乳剂,并应用所选择的技术参数开展了针对性试验研究,效果较好,保证原油脱后含盐指标完成,为单炼流花原油提供了设计依据.     

胜利油田纯梁原油乳状液稳定性研究

利用LUMisizer LS610稳定性分析仪研究了胜利油田纯梁原油乳状液的稳定性和液滴直径的变化规律,考察了不同结构破乳剂对乳状液稳定性的影响。结果表明,在离心力的作用下,大液滴沉降得更快,导致靠近样品池底部位置的透光率偏高,大液滴较多。直链的非离子破乳剂BP01吸附能力较强,在低质量分数时即表现出高效的破乳能力;支链非离子破乳剂PA05由于其特殊的支链结构,吸附能力较弱,对乳状液的破坏能力略弱于BP01;阳离子破乳剂HY01在离心力场中对乳状液稳定性的影响不明显。     

中原油田原油交联复配破乳剂的研制及应用

中原油田采油三厂卫城原油破乳脱水难,长期未能得到彻底的解决。针对卫城原油高含胶质、粘度大等特点,实验测定了南京金钟山化工厂、山东滨州化工厂等厂生产的8种破乳剂及其交联复配而得的6种破乳剂对中原油田卫城原油的脱水效果。结果表明,6种交联复配破乳剂脱水率高,脱水速度快,油水界面齐,与卫城原油的缓蚀剂配伍性好。油溶性破乳剂ZF006（浓度为90mg/l）在明一联3个月的现场试验结果表明,净化油的含水量降低了41．3％,污水含油降低了40．8％。     

不同结构破乳剂对原油乳状液的适用性研究

采用大庆油田采油四厂杏二中原油和污水,在室内配制原油乳状液,研究了不同结构破乳剂（SP169、BP169—21、AE9901、AR36、AP221、TA1031）及其浓度对不同矿化度原油乳状液的适用性。结果表明：AR36脱水速度最快、水色清、油水界面清晰,最大脱水率为88％,适用于大庆杏二中原油乳状液的脱水;AE9901的脱水率为729／6,SP169为70％,TA1031为64％,BP169-21为58％,AP221为54％。AR36存在最佳使用浓度（200mg／L）;SP169、AP221脱水率随浓度的增加而增大。破乳剂浓度增加,可降低油水界面黏度,减弱界面膜强度,从而提高脱水效率。AR36脱水率随矿化度增加而增大,适用于高矿化度乳状液脱水;BP16921脱水率随矿化度增加而减小,不适合高矿化度乳状液脱水。其它4种破乳剂的脱水效率与矿化度无对应关系。     

Tuning of properties of alkyl phenol formaldehyde resins in petroleum demulsifiers. 2. Interfacial dilatational properties

In the context of the study of crude oil dehydration, two hydrophilic ethoxylated phenol formaldehyde polymeric resins with different degrees of ethoxylation 10 (PR_A) and 20 (PR_B) were studied at the oil/water interface. Viscoelastic properties of model monolayers were obtained by frequency sweep tests, using a drop tensiometer and axisymmetric drop shape analysis. Overall, a significant gap was measured between the values of elastic modulus of PR_A and PR_B monolayers, and the experimental data showed a good correlation with the Lucassen and Van den Tempel model. These results indicate that interfacial intramolecular interaction appear stronger for resin PR_B likely related to its hydrophobic structure favoring surface active properties. On the other hand, PR_B has shown a better ability than PR_A to destabilize crude oil monolayers and better demulsifying properties, counteracting the effect of asphaltenes as stabilizers. This study allows a better understanding of the demulsifying properties of such resins.     

梳状硅破乳剂的溶液性质

采用氢硅加成法,用不同含氢量的含氢硅油和聚醚制备得到了一系列具有梳状结构的非离子有机硅聚醚破乳剂(PESO).利用红外光谱对产物的结构进行了表征,采用表面张力、界面张力、粒度和破乳对PESO破乳剂进行性能检测.结果表明:随着含氢硅油(PHMS)含氢量的增加,PESO破乳剂的平均粒径增大且分布变宽,破乳性能减弱.当PHMS含氢量由1.6%降至0.18%时,CMC由0.808g/L降至0.646g/L,γCMC可降至22.03mN/m,脱水率高达85%.     

BAHA非聚醚型破乳剂的合成及破乳效果

根据原油的特性和破乳机理,设计合成了具有适宜芳香度和极性的BAHA非聚醚型破乳剂,该 剂具有较强的增溶、絮凝、击破界面膜的能力。试验数据表明,该剂具有适宜极性(PHA=13～18)时, 对三元复合驱模拟采出液具有较好的破乳脱水效果。