低渗透油藏在水驱开发中存在地层能量不足和注水困难的问题.一方面注水压力高、欠注严重;另一方面地层压降大、产能递减快,采油速度和采出程度低,水驱过后依然存在膜状或油滴状等多种形态的残余油.针对上述问题,以环氧氯丙烷、十二烷基叔胺、甲硝唑等为原料制得甲硝唑不对称Gemini型表面活性剂,将其与脱氢松香型表面活性剂、鲸蜡醇、乙醇等复配制得功能型增注驱油剂.研究了功能型增注驱油剂的乳化能力、润湿性、防膨性、降压增注及驱油效果等,并在渤南油田进行了现场应用.结果表明,该功能型增注驱油剂不仅可以吸附在油水界面降低油水界面张力,还可以乳化原油、清除油膜,并且其中的阳离子组分以水为传递介质在岩石表面形成分子膜,稳定黏土,改善岩石表面润湿性,降低注入压力、提高注水采收率.功能型增注驱油剂在较低浓度时即有较好的防膨效果,其降压增注及驱油效果较好.在压驱现场试验中,注水井的注入能力和对应油井的产油能力显著提高.

曲9-21块储层敏感性较强,具有中等偏强水敏,且泥质含量较高,目前区块注水量低,难以实现有效注水.为解决注水开发过程中黏土矿物遇水膨胀问题,通过室内实验,开展区块注入水水质现状分析、注入水结垢趋势预测以及地层水与注入水配伍性研究;利用钠基膨润土评价曲9-21区块前期应用防膨缩膨体系及配方优化,优选出缩膨率较高的体系;通过岩心实验,模拟井下环境完成岩心动态渗透率伤害恢复分析,筛选适合该区块的防膨缩膨体系.

为了提高低渗透油藏注水井的降压增注效率,本文研究了岩石表面润湿性、界面张力等因素对低渗透油藏注水阻力的影响规律,并在此基础上研究了一种多功能型减阻增注剂CNG,评价了CNG溶液改变油水界面张力、改变岩石表面电性和润湿性和改变岩心降压增注效果的能力.研究结果表明:CNG既能降低油水界面张力至10-3 mN/m数量级、消除岩心毛管阻力;又能吸附在岩石表面消除岩石表面负电荷、改善岩石表面润湿性至弱水湿.CNG即适用于含有残余油的岩心降压增注,又适用于强水湿油藏的减阻增注,还适用于即有残余油又强水湿油藏的降压减阻增注.对于胜利油田某区块天然岩心,CNG用于不洗油的原始岩心时,渗透率提高48.49％,驱替压差降低31.25％;CNG用于没有残余油、呈现水润湿状态的岩心时,渗透率提高36.32％,驱替压差降低27.66％.

目前广泛使用的杀菌剂是以季铵盐为主的复配杀菌剂.针对目前常规杀菌剂和聚合物发生反应失活导致含聚污水杀菌效果差、硫酸盐还原菌(SRB)达标率低等问题,设计合成了硫酸酯-双季铵盐型杀菌剂,并通过红外、核磁和元素分析对其进行了结构表征.该杀菌剂既具有高效杀菌功能基团,又具有阴离子防聚沉基团.性能评价显示:该杀菌剂浓度为50mg/L时,40℃下杀菌4h,培养7天后细菌浓度为0;同时该杀菌剂和聚合物没有聚沉现象,对含聚污水的浊度和黏度都没有影响.在孤六联进行了现场试验,现场试验区SRB菌控制在25个/mL以下,水质符合SY/T5329-2012标准要求.

Corrosion inhibitors (Glycine, N-[N-[(phenylmethoxy) carbonyl] glycyl]-, 4-nitrophenyl ester (A), Nα,ω-Dicarbobenzoxy-L-arginine (B), N-(2-benzoylphenyl)-1-benzyl pyrrolidine-2-carboxamide (C), Eth...

针对目前常规杀菌剂和聚合物发生反应失活导致含聚污水杀菌效果差、硫酸盐还原菌(SRB)达标率低等问题,成功设计、合成了硫酸酯-双季铵盐型杀菌剂,并通过红外、核磁和元素分析对其进行了结构表征.性能评价结果显示:该杀菌剂的质量浓度为25 mg/L时,杀菌效率接近100％;同时该杀菌剂和聚合物没有聚沉现象,对含聚污水的浊度和黏度都没有影响.扫描电镜照片显示,硫酸酯-双季铵盐型杀菌剂和1227阳离子型杀菌剂的杀菌机理不同.在孤六联进行了现场试验,现场试验区SRB控制在25个/mL以下.

为深入研究酸化缓蚀剂的缓蚀作用机理,将实验方法与量子化学、分子动力学相结合分析缓蚀剂分子结构与缓蚀率之间的关系.采用挂片失重法测得五种酸化缓蚀剂甘氨酸,N-[N-[(苯甲氧基)羰基]氨基乙酰基]-,4-硝基苯酯(A)、Nα,Nω-二苄氧羰基-L-精氨酸(B)、(R)-2-[N-(N-苄基脯氨酰)氨基]二苯甲酮(C)、4-[(4-甲氧亚苄基)氨基]肉桂酸乙酯(D)、5-羟基色氨酸(E)在15％HCl溶液中的缓蚀率,并用金相显微镜观察了腐蚀后N80钢挂片的3D形貌,最后用量子力学和分子动力学相结合的模拟方法对5种缓蚀剂的缓蚀性能进行了理论分析.结果表明,5种酸化缓蚀剂的缓蚀率均大于93％,酸化缓蚀剂缓蚀效果按缓蚀率大小排序为:B>A>D>C>E,按平均点蚀深度排序为:B>A>D>C>E,按最大点蚀深度排序为:A>B>D>C>E,其中B、D抑制点蚀效果较差;通过量子化学计算得到的酸化缓蚀剂缓蚀性能从大到小依次为:A>B>D>C>E,通过分子力学计算得到的缓蚀性能从大到小依次为:A>B>C>D>E,理论分析与实验结果基本相符.

The effective period of molecular membrane injection technique depended on the molecular adsorption performance onto the surface of reservoir rock. In order to prolong the effective period of molecular membrane injection technique,the adsorption of some cationic compounds onto the rock surface was simulated by the method of molecular mechanics and Monte Carlo. According to the results of molecular simulation,the three quaternary ammonium of alkyl fatty amine polyoxyethylene ether(AFATQA)was designed as a new molecular film injection agent. Its adsorption energy and drag reduction effect were calculated. Then AFATQA was synthesized and the structure of synthetic product was characterized. Its comprehensive performance evaluation was carried out by laboratory experiments,and the molecular membrane composite measure was implemented in Shengli oilfield. Molecular simulation results showed that the single molecule adsorption energy increased with the increase of hydrophobic chain length or charge density. Acyl amine groups and hydroxyl could improve the single molecule adsorption energy. It simulated that AFATQA had a high adsorption energy(-155.51 kcal/mol)and a significantly drag reduction effect. The synthesized AFATQA based on the disigned model could adsorbed on the surface of rock. The Zeta potential and the contact angle increased on the surface of rock with increasing AFATQA concentration,AFATQA's swelling rate also increased. The core flooding experiment results showed that AFATQA could effectively reduce the injection pressure. After the molecular film composite measure was applied in L37-34 well, the increasing injection effect was obvious. It showed that the water injection increased,the water injection pressure reduced,the corresponding oil production increased,water content decreased and the dynamic liquid level rose.

The displacing phase change usually leads to unstable polymer absorption of polymer injection layer and serious injection pressure fluctuations, thus resulting in varied differential pressure and flow between layers and frequent flow measurement and regulation. To address the issue, the self?diverting downhole pressure regulation pol?ymer injection technology has been studied. The technology could achieve self?diverting and pressure regulation of high and low pressure layers and maintain stable diversion ratio by means of downhole low shear force self?diverting device, eliminating the need for later separate layer regulation. Indoor and field test results show that the pressure regulation polymer injection technology with the flow diversion ratio of 2∶1 and 3∶1 has been formed, achieving layer injection with distribution ratio. The tool could also make pressure compensation while the injection layer pres?sure fluctuating and maintain the injection amount constant, thus achieving efficient injection of separate layer of polymer injection well.

To achieve reasonable allocation and stable regulation of water injection in injection wells with large differential pressure in middle and high permeability reservoirs, a real-time adjusting water distributor is designed by using dynamic throttling pressure regulating principle of spring-piston system. The regulating performance of this distributor is simulated with Simulink and ADAMS by building an appropriate mechanical model, and its main dy-namic adjusting characteristics are investigated, including the initial adjusting pressure, effective movement region and stabilization time. In addition, the pressure wave pattern, spring stiffness and piston cross-sectional area are optimized. Simulation results show that, the larger the spring stiffness of water distributor, the shorter time it takes for the system to become stable; the piston displacement is decreased as the spring stiffness is increased with differ-ent spring stiffness, and with different cross-sectional areas of the piston right side, the piston displacement is de-creased as the area is decreased. The simulation results could provide basis for the series design of real-time adjus-ting and distributing mechanism in the future.

为提高低渗透油藏的增注效果,研制开发了新型MDG系列分子膜增注剂.通过室内实验对3种分子膜剂BFS、BNFS和TD12的润湿性、表面活性、耐温耐盐性能等进行了评价.实验结果表明,该系列分子膜剂具有良好的改变润湿性的能力和表面活性,以及较好的耐温、耐盐性能.BFS、BNFS和TD12耐温120℃,耐盐40 000 mg/L,其最低使用质量浓度分别为200,500,800 mg/L.

针对低渗透砂岩油藏储层低孔低渗导致注水压力高、欠注严重等问题,研制了带有酰胺基的阳离子双子表面活性剂BNFS（分子膜增注剂）。评价了BNFS的吸附性能、润湿性能、表界面活性及减阻性能,结果表明BNFS在砂岩表面吸附后形成分子膜层,岩心表面接触角从27.6°增至88.6°,由强亲水转为弱亲水。BNFS浓度为200mg/L时,溶液的表面张力为26.61mN/m,与煤油间的界面张力为0.06mN/m。岩心驱替实验表明,BNFS处理后,砂岩岩心的水相渗透率提高80%~120%,注水压力降低12%~18%。增注机理分析结果表明,在靠近孔壁处,分子膜增注剂、水与孔壁作用能级分别为10 -18 、10 20 J,分子膜增注剂与孔壁的综合作用能远大于水分子,在竞争吸附中占绝对优势,使有效渗流通道增加。BNFS处理岩心后,岩心-水的黏附功由136.5mN/m降至75.7mN/m,减阻作用明显。图5表1参7

Hydroxyethyl cellulose (HEC) pervaporation membranes were employed for the desulfurization of fluid-catalytic-cracking (FCC) gasoline. Based on solution-diffusion mechanism, the solubility of sulfur during the pervaporation process was studied by carrying out experiments and modeling, and UNIFAC-FV, UNIFAC-ZM, and Entropic-FV models were compared. The results show that the prediction by UNIFAC-FV model is more accurate than the other two models, especially when the sulfur mass fraction in the feed is <4000μgg−1. The mass fraction of sulfur adsorbed onto the polymer surfaces increases with increasing temperature and sulfur content in the feed, and the latter is more effective than the former. The distribution coefficients of thiophene and n-heptane were calculated by using UNIFAC-FV model, and further compared to the experimental results.

Aiming at the problems of high water-injecting pressure and water-injecting difficulty,organic molecular membrane injecting agents were developed for low permeable sandstone reservoir.The drag-reducing effects and wash-resistant ability of three kinds of molecular membrane injecting agents(BFS,BNFS,and TD12) were evaluated by core-flooding experiment and continuous wash test.The results showed that the water permeability of the cores treated by molecular membrane injecting agents increased at different levels.Drag-reducing effects were different while the structures of molecular membrane injection agents were different at different levels.The water permeability of three cores had no obvious change when the total injecting amount was more than 260 PV,which showed that the core had good wash-resistant ability after the micro-channel wall of the core adsorbed the molecular membrane injecting agents.

Three kinds of augmented injection technologies of reservoir surface modification by using shrinking agent,nanometer polysilicon and surfactant are summarized,and the features,mechanisms of drag reduction and application of the technologies are introduced.

In view of the blockage of water injection well,a new emulsion type plug removal agent was developed.According to the results of laboratory study and field test,this emulsion type plug removal agent has good retarding capacity and high surface activity,and therefore it can eliminate the blockage of reservoir caused by inorganic and organic scales and is useful for plug removal and injection augmentation.

A composite membrane was prepared through pre-wetting method using poly(ethylene glycol) (PEG) as active layer and poly(vinylidene fluoride) (PVDF) as microporous support layer. When the solid content in active layer solution was up to 16%,the pore penetration occurred at a low level and the permeation flux increased. Effects of feed temperature,feed flow rate and permeate pressure on pervaporation performance were investigated. The sulphur enrichment factor increased firstly and then decreased with increasing feed temperature and flow rate,and met its peak value at 100 ℃ and 100 mL/min. The permeation flux increased with increasing temperature,and decreased with increasing flow rate greater than 100 mL/min. Both the sulphur enrichment factor and flux decreased with increasing permeate pressure. For typical fluid catalytic cracking gasoline feed,the permeation flux and sulphur enrichment factor came to 2.7 kg/(m2·h) and 3.6,respectively.

The different composite hydroxyethyl cellulose(HEC)/ polyvinylidene fluoride(PVDF) membranes were prepared by coating method.The effect of the polymer content in casting solution on the structure of composite membranes was studied.the desulfurization performance of composite HEC membranes was tested using fluid catalytic cracking gasoline.The results show that the increasing of polymer concentration in the casting solution reduces the mean pore radius and porosity of support layer,and the diffusion and mass transfer coefficient of gasoline components in the support layer,but increases the ratio of the mass transfer coefficient between methyl-thiophene and octane.This would lead to a decrease in permeation of composite HEC membrane and an increase in selectivity.If polymer concentration further increases,the average pore radius is very small so to lead to a capillary condensation.Consequently,the membrane selectivity reduces and the permeation increases.

The effect of crosslinking on desulfurization mechanism was investigated by the study of sorption and diffusion behaviors of typical gasoline components through the hydroxyethyl cellulose (HEC) membranes with different crosslink density. The sorption, diffusion and permeation coefficients of gasoline components were calculated in the membranes. The results showed that the diffusion mode of typical gasoline components n-heptane and cyclohexane in the HEC membranes tended to non-Fickian, but the diffusion kinetic of thiophene, toluene and cyclohexene was typical Fickian. The increasing crosslink density did not change the transport mode of gasoline components in HEC membranes but severely reduced the HEC–gasoline components interaction. Although the sorption and diffusion rates decreased, the difference of sorption/diffusion rates between sulfur and non-sulfur compounds increased with increasing crosslink density, predicting that permeation flux decreased but sulfur enrichment factor increased. The effect of crosslinker content on pervaporation performance of HEC membrane was studied, and the change regularity of flux and sulfur enrichment factor corresponded to the theory analysis results on dynamic sorption curves. Thiophene species had higher sorption and diffusion rates in the HEC membranes than other hydrocarbon components and were the preferential permeation components. These were verified by gas chromatography analysis results of feed and permeate samples of real gasoline.

In order to further improve the desulphurization capability of hydroxyethyl cellulose(HEC) membrane,5 kinds of HEC with different molecular weight were modified through the crosslink.The effect of molecular weight and crosslinking agent on the desulphurization properties of HEC membrane was studied.The results show that the HEC with an inherent viscosity of 122 mL/g is suitable to use for FCC desulphurization.Next,the desulphurization properties of HEC membrane vary with the crosslinking agent type.The obtained membrane was used for pervaporation test.It is found that enrichment factor first increases and then decreases with the increasing operating temperature and has a maximum at so called optimal desulphurization temperature.The optimal desulphurization temperature depends on feed type.