聚醚类破乳剂的界面扩张流变性质

采用悬挂滴方法研究了不同结构聚醚类破乳剂与煤油间的界面张力及界面扩张流变性质. 结果表明, 4种聚醚类破乳剂均具有较强的降低界面张力能力, 且支链化程度越低分子在界面上排列越紧密, 直线型破乳剂在低浓度条件下界面张力最低. 破乳剂的分子尺寸较大, 慢弛豫过程控制界面膜性质, 吸附膜以弹性为主. 同时, 柔性聚氧乙烯链和聚氧丙烯链对界面膜性质的影响较大, 随着支链化程度增大, 界面分子间相互作用增强, 界面膜弹性增强, 黏性降低.     

破乳剂对复合驱乳状液的破乳机理研究

针对模拟采出液和三元复合驱矿场采出液,研究了破乳剂对复合体系界面张力和膜强度的影响.破乳剂浓度增加,二元复合体系界面张力降低,而三元复合体系界面张力升高.破乳剂分子部分顶替乳化剂分子并显著降低了界面膜强度.     

聚表剂驱模拟采出液油水界面性能研究

通过考察聚表剂对大庆油田聚表剂驱模拟采出液油水界面张力、油水界面扩散双电层zeta电位、界面粘弹性以及界面膜强度的影响,研究聚表剂对聚表剂驱模拟采出液油水界面性能的影响规律。结果表明:具有表面活性剂和聚合物双重性能的聚表剂利用其两亲性质在油水界面吸附,形成稳定的界面膜,使油水界面张力降低,界面膜强度增加;且随聚表剂浓度增加,油水界面张力降低,界面膜强度增加。在所研究的四种聚表剂类型中,海博Ⅲ(O/W)型聚表剂改善油水界面性能的效果较为突出。     

不同结构破乳剂油水界面扩张粘弹性研究

研究了支链破乳剂AE121和直链破乳剂SP169在正癸烷-水界面上的扩张粘弹性质,阐述了两种破乳剂扩张模量随扩张频率和破乳剂浓度的变化规律,考察了两种破乳剂对原油活性组分界面扩张性质的影响,测定了两种破乳剂的水溶液与正癸烷的动态界面张力,并与界面扩张流变性质进行了关联.研究结果表明,两种破乳剂的加入均会大大降低原油活性组分界面膜的扩张模量.较低浓度下直链破乳剂SP169由于吸附能力稍强,降低扩张模量效果较好；而一定浓度以上支链破乳剂AE121由于顶替能力较强,具有一定优势.由于破乳剂本身具有一定的扩张模量,在降低界面扩张模量的效果上,破乳剂的用量并非越大越好.     

表面活性剂对驱油聚合物界面剪切流变性质的影响

利用双锥法研究了表面活性剂十二烷基苯磺酸钠(SDBS)和十六烷基三甲基溴化铵(CTAB)对油田现场用部分水解聚丙烯酰胺(PHPAM)和疏水改性聚丙烯酰胺(HMPAM)溶液的界面剪切流变性质的影响,实验结果表明:HMPAM分子通过疏水作用形成界面网络结构,界面剪切复合模量明显高于PHPAM.SDBS和CTAB通过疏水相互作用与HMPAM分子中的疏水嵌段形成聚集体,破坏界面网络结构,剪切模量随表面活性剂浓度增大明显降低.同时,界面膜从粘性膜向弹性膜转变.低SDBS浓度时,少量SDBS分子与PHPAM形成混合吸附膜,界面膜强度略有升高;SDBS浓度较高时,界面层中PHPAM分子被顶替,吸附膜强度开始减弱.阳离子表面活性剂CTAB通过静电相互作用中和PHPAM分子的负电性,造成聚合物链的部分卷曲,从而降低界面膜强度.弛豫实验结果证实了表面活性剂破坏HMPAM网络结构的机理.     

Zeta电位和界面膜强度对水包油乳状液稳定性影响

通过对表面活性剂、聚合物溶液和煤油体系油水界面剪切黏度和油珠的Zeta电位的测定,考察了界面膜强度和Zeta电位对水包油乳状液稳定性的影响。在煤油、表面活性剂、聚合物聚丙烯酰胺(3530S)或其氧化降解聚合物体系中,含有3530S时,界面膜强度值最大,最大值大于0.10 mN/m,Zeta电位为-18.4 mV,绝对值最大,乳状液最稳定。结果表明,油水界面膜强度和油珠表面的Zeta电位对水包油乳状液稳定性影响较大。界面膜强度和Zeta电位绝对值较大时,乳状液最稳定;当界面膜强度相差不大时,Zeta电位绝对值大的乳状液较稳定,此时双电层对乳状液稳定性起主要作用;当Zeta电位相差不大时,界面膜强度大的乳状液较稳定,此时界面膜强度对乳状液稳定性起主要作用。研究还表明,机械或氧化降解后的聚合物体系,界面剪切黏度和Zeta电位绝对值变小,乳状液稳定性变差。     

环烷酸对油水界面膜流变性质的影响研究

研究了环烷酸对油水界面膜界面张力、弹性模量、损耗模量以及界面膜破裂速率常数的影响,同时对环烷酸与沥青质之间的相互作用进行了测定。结果表明,环烷酸使得原油油水界面张力下降;弹性模量随着环烷酸加量以及振荡频率的增加都分别逐渐增大,并且最终都趋于平衡;在任何振荡频率值时,损耗模量都随着环烷酸加量先增大后减小;当环烷酸加量增加时,界面膜破裂速率常数降低。环烷酸与沥青质之间存在相互作用,随着环烷酸加量的增加,其对沥青质界面膜弹性模量的影响与对原油界面膜弹性模量的影响相似,表明环烷酸主要是通过与沥青质相互作用而促进乳状液稳定性的。     

支状嵌段聚醚的界面聚集行为及对原油乳状液的破乳作用

合成了三种不同聚氧丙烯/聚氧乙烯(PPO/PEO)比例的含苯环支状嵌段聚醚, 通过界面张力、界面流变、表面压以及对原油乳状液的破乳脱水效果的测定, 考察了其界面聚集行为和破乳作用对PEO含量和分子量的依赖性, 并且对比研究了三种支状聚醚分子交联前后的破乳性能. 结果表明, PEO含量高且分子量大者,其单分子界面占据面积大, 在油/水界面达到吸附平衡的时间短, 其油/水界面扩张模量及扩张弹性均高于PEO含量较少者. 但是对原油乳状液的破乳脱水效果则是PEO含量居中的聚醚最好. 温度影响和交联与否的研究表明, 交联并不能提高分子量较大的聚醚对原油乳状液的破乳效果, 温度对聚醚分子交联前后的破乳效果有不同的影响规律. 本研究可为原油集输过程中化学品的选择与应用提供一定的依据.     

界面张力弛豫法研究不同结构破乳剂油水界面扩张粘弹性

采用界面张力弛豫法研究了支链破乳剂AE121和直链破乳剂SP169在正癸烷-水界面上的扩张粘弹性质，并与小幅周期振荡法获得的结果进行了比较.阐述了两种破乳剂的扩张模量随扩张频率和破乳剂浓度的变化规律.研究发现，在低频率处，两种破乳剂的扩张模量均接近于零；在中间频率范围内，扩张模量随扩张频率的增加而增大；在高频率处，扩张模量的幅度接近于极限扩张弹性.在中间频率范围内，扩张模量随破乳剂浓度增大，在接近临界胶束浓度处出现一个极大值；同时还发现，界面上和界面附近的微观弛豫过程的数目随破乳剂浓度增加而增大，其贡献也呈规律性变化.     

短链烷基对多取代烷基苯磺酸盐界面性质的影响

利用悬挂滴方法研究了2,5-二乙基-4-壬基苯磺酸钠(292)、2,5-二丙基-4-壬基苯磺酸钠(393)和2,5-二丁基-4-壬基苯磺酸钠(494)在空气-水表面和正癸烷-水界面的扩张流变性质,考察了时间、界面压、工作频率及体相浓度对扩张弹性和粘性的影响。研究发现,在低表面活性剂浓度条件下,表面吸附膜类似弹性膜,其强度由膜内分子的相互作用决定;高浓度下体相与表面间的扩散交换过程控制表面膜的性质。油分子的插入导致界面吸附分子之间相互作用的削弱,扩散交换过程主导界面膜性质;但随着短链烷基长度增加,油分子的影响变小。表面膜的强度在吸附达到平衡前已经决定,而界面膜在吸附饱和后仍然随界面分子重排而变化。     

Influence of demulsifier on interfacial film between oil and water

Demulsification of a synthetic water in oil (W/O) crude oil emulsion was studied by measuring water–oil interfacial properties such as life time and thinning rate of oil film in the presence of various demulsifiers. The results indicated that the interfacial elasticity decreased both the strength and the life time of oil film and film thickness when adding the demulsifiers. The oil film broke when film thickness came to a critical level. As for a demulsifier, the interfacial elasticity was decreased with demulsifier concentration increase, and stayed constant above a critical demulsifier concentration. The rate of dewatering is related to interfacial elasticity. When different demulsifiers were compared, the more the interfacial elasticity was lowered, the more efficient was the dewatering. The mechanism of the different types of demulsifiers was discussed based on the experimental results. The demulsifiers partially replaced the emulsifiers, which led to the interfacial elasticity decreased. The effect of chemical structure of the demulsifiers on water–oil interfacial film was studied.     

Effect of Demulsifiers on Dilatational Properties of Crude Oil–Water Interfaces

The dilatational properties of polyether demulsifiers PEA, PEB, PEC, PED, PEF, and PEG at the decane-water interface were investigated. Meanwhile, the effect of demulsifiers with different structures on interfacial dilatational modulus of diluted crude oil also was explored. The properties of demulsifiers are compared and analyzed in combine with the dilatational parameters at decane-water interface and at 5% crude oil-water interface. The results show that interfacial dilatational viscoelasticity could characterize the interfacial behavior of demulsifiers. The demulsifiers, which have different kinds or structures, have different effects on destroying the interfacial film of crude oil with increasing bulk concentration. Therefore, the dosage of demulsifier is a very important role in controlling nature of crude oil film.     

Effect of Demulsifier Structures on the Interfacial Dilational Properties of Oil–Water Films

The dilational properties of a branch-shaped polyether-type nonionic demulsifier (PEB), a comb-shaped polyether-type nonionic demulsifier (PEC), and a star-shaped polyether-type nonionic demulsifier (PES) at the decane–water interfaces were investigated by Langmuir trough method through oscillating barrier and interfacial tension relaxation methods, which are mainly in the influences of oscillating frequency and bulk concentration on dilational properties. Meanwhile, the effect of demulsifiers on interfacial dilational modulus of diluted crude oil was also explored. The experimental results indicate that all demulsifiers can decrease the dilational modulus of diluted crude oil at the experimental concentration. The addition of PEB causes the dilational modulus of crude oil to be lower than that at the water–decane interface. The demulsifier PEC has a similar effect with PES to influence the interfacial film of crude oil: at low concentration, the dilational modulus of mixed interfacial film is lower than that of demulsifier alone, while at high concentration, the dilational modulus of mixed interfacial film is slightly higher than that of demulsifier alone. The dependence of static modulus on the bulk concentration is consistent with the trend of interfacial dilational modulus with concentration for demulsifiers PEB, PEC, and PES. The studies about the structure modulus show that the new demulsifiers PEC and PES have a stronger ability than branch-shaped demulsifier PEB to destroy the interfacial film.     

Interfacial Dilational Properties of Two Different Structure Demulsifiers at Oil–Water Interfaces

The dilational properties of demulsifiers PE1 and PE2 at the decane-water interface were investigated. Meanwhile, the influence of demulsifiers on interfacial dilational modulus of 5% crude oil also was explored. The experimental results indicate that the diffusion process is still not the main factors to control the properties of interfacial film even at large concentration. The dilational modulus of demulsifier PE2 passes through a maximum with the increasing concentration, and that of demulsifier PE1 changes a little with the increasing concentration at the decane-water interface. The dilational moduli of crude oil inerfaces decrease with the addition of both demulsifiers. At low concentration, the effect on reducing the dilational modulus of crude oil is stronger for PE1, which maybe caused by its higher substitution ability. For PE2, the ability to decrease interfacial dilational modulus gets stronger with increasing bulk concentration, which might be explained by that the adsorption increases with increasing concentration. The results of relaxation experiments support those obtain by oscillating barriers method.     

A study of interfacial dilational properties of two different structure demulsifiers at oil-water interfaces

The interfacial dilational viscoelastic properties of two demulsifiers with straight chain (SP-169) and branched chain (AE-121) at the oil-water interfaces were investigated by means of the longitudinal waves method and the interfacial tension relaxation method, respectively. The results obtained by the longitudinal waves method showed that the dilational viscous component for AE-121 and SP-169 also passed through a maximum value with increasing concentration. It was found that the maximum value appeared at different demulsifier concentrations during our experiment frequency; and the higher is the dilational frequency, the lower is the concentration. The influences of AE-121 and SP-169 on the dilational viscoelastic properties of the oil-water interface containing surface-active fraction from Iranian crude oil have been measured. The results clearly stated that both demulsifiers could obviously decrease the dilational elasticity of oil-water interface containing surface-active fraction. At low concentration, because of stronger adsorption ability, SP-169 has stronger ability to decreasing the dilational modulus than AE-121. We also found that the dilational modulus of the interface contained surface-active fraction passed through a minimum value with increasing demulsifier concentration for both demulsifiers. This result indicated the dosage of demulsifier had an optimum value. The results obtained by means of interfacial tension relaxation method showed that the slow relaxation processes involve mainly rearrangement in the conformation of the molecules appeared with increasing demulsifier concentration.     

Demulsification and Interfacial Properties of Crosslinking Phenol-Amine Resin Block Polyether Demulsifiers

Six novel crosslinking phenol-amine resin block polyether demulsifiers were synthesized for demulsification of surfactant-polymer flooding emulsion. The demulsification performances of these demulsifiers were investigated by conventional graduated bottle test. Their interfacial behaviors at water-oil interface were explored by dynamic interfacial tension and interfacial dilational viscoelasticity measurements. The results show that the demulsification efficiency is dependant on the hydrophilic-hydrophobic balance (HLB) value of these demulsifiers. It was also correlated to the interfacial activity and the dilational elasticity at the water-oil interface. The higher the HLB value of demulsifiers, the better the demulsification efficiency is.     

疏水改性聚丙烯酰胺对原油组分界面扩张流变性质的影响

利用悬挂滴方法研究了疏水改性聚丙烯酰胺(HMPAM)对胜利采油厂高温高盐油藏采出原油中酸性活性组分和沥青质界面膜扩张流变性质的影响,考察了不同活性组分浓度条件下的界面扩张流变行为.实验结果表明:1750mg·L-1HMPAM能够在界面上形成网络结构,界面扩张模量数值高达100mN·m-1左右;油相中的酸性组分随着老化时间增加吸附到界面上,与HMPAM分子的疏水改性部分形成聚集结构,一方面通过快速的扩散交换过程大大降低扩张模量,另一方面通过与疏水改性部分的相互作用加强HMPAM分子间的缔合强度,增强网络结构的弹性.沥青质分子尺寸相对较大,分子间存在氢键等较强的相互作用,造成沥青质界面聚集体和HMPAM形成的网络结构共同决定界面膜性质,混合膜的扩张模量较单独HMPAM体系仅略有降低.     

Distribution of Demulsifiers between Crude Oil and Water phases

Using a radiosoptopic tracer to measure the concentration of demulsifiers,we studied the distribution regularity of demulsifiers between crude oil and water phases under different temperatures and found that the dewatering rate is related to the partition coefficient of demulsifier, which is quite sensitive to the variation of temperature According to the experimental results, we hold that an effective demulsifier should possess a relatively high partition coefTicient.