破乳剂对油水界面膜作用机理研究

研究了破乳剂存在下油膜寿命、油膜薄化速率以及油水界面性质与破乳效果的关系.结果表明,破乳剂使油水界面弹性降低,导致油水界面强度减弱,界面膜寿命变短,界面膜厚度变薄.当膜厚度变薄到一临界值时,膜破裂,导致破乳脱水.同种破乳剂,随着其浓度的增加,界面弹性降低.当浓度超过某一值时,界面弹性值基本不变.不同种破乳剂,界面弹性降低幅度越大,其破乳效果越好.界面弹性值可以很好解释破乳剂的脱水率变化规律.     

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.     

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.     

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.     

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.     

Influence of Asphaltene Concentration on the Interfacial Properties of Two Typical Demulsifiers

Oil-in-water emulsion is an innovate manner by which heavy crude oil can be transported from producing sites to transforming sites through pipelines. The effect of emulsifier on the interfacial properties and demulsification performance of demulsifier for heavy crude oil–in-water emulsion has been studied by many researchers. However, the influence of asphaltene in heavy crude oil on the interfacial properties of demulsifier has not been investigated yet. In this article, the influence of asphaltene concentration of two typical demulsifiers (straight-chained SP-1 and branch-chained AE-1) was systematically studied in terms of absorption thermodynamics, absorption kinetics, and coalescence kinetics. The results revealed that the demulsifier adsorption was a ΔS controlled spontaneous process. The absolute value of ΔG of SP-1 adsorption was found to decrease with asphaltene concentration, whilst the asphaltene concentration had no significant influence on that of AE-1. With the increase of asphaltene concentration, the demulsifiers’ adsorption rates increased, but the reorganization rates on the interface decreased. Coalescence speed of asphaltene droplet decreased with asphaltene concentration in spite of demulsifier type. Additionally, AE-1 had higher absolute value of ΔG, adsorption speed, and coalescence speed than that of SP-1 at the same condition.     

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.     

新型高效原油破乳剂PNT-05的研制与应用

针对中原油田采油六厂二区原油破乳脱水过程中存在的脱水速度慢,乳化中间层厚等问题,通过分子结构设计手段,在非离子型破乳剂基础上,经酯化,在破乳剂分子中引入阳离子基团,合成出季胺盐阳离子型破乳剂PNT－05,利用季胺盐阳离子型破乳剂与助剂复配的方法室内解决了中原油田二区原油破乳脱水过程中顾在的问题,与油田现场用破乳剂相比,新的破乳剂体系脱水速度快,脱水效率高,使乳化中间层变薄或消失,同时探讨了季胺盐阳离子型破乳剂PNT－05的作用机制。     

Enhanced sedimentation and coalescence of petroleum crude oil emulsions by the new generation of environmentally friendly yellow chemicals

This study compares by means of new and advanced destabilization protocols the efficiency of new chemistry environmentally friendly (yellow) demulsifiers with already commercially available red demulsifiers in destabilizing two types of water-in-oil (w/o) emulsions: petroleum crude oil emulsions and model dense packed layers (DPLs). Oil–water separation profiles were measured by low-field nuclear magnetic resonance (NMR), which allows monitoring the water content as well as the mean droplet size in the emulsion as function of the sample height and the time. Separation profiles measured by NMR depicted an increase of the free water release kinetics as the concentration of demulsifier as well as the sedimentation rate increased. The water resolution was not substantially improved by increasing the concentration further while the water quality was worse, most likely due to adsolubilization. There was no observation of DPL formation in these crude oil emulsions. Four different demulsifiers were tested on a model DPL and compared with normal crude oil emulsions. One chemical showed higher efficiency in destabilizing DPL than destabilizing crude oil emulsion. The interfacial rheological properties for one of the systems showed a slight increase in the elastic modulus (E′), as the concentration of demulsifier increased. The increment of the elastic modulus is not totally understood. The most central parameters were represented by principal component analysis (PCA). PCA did not contribute in a better characterization of the chemicals. The new-generation yellow demulsifiers did not reproduce the efficiency of commercially available, less environmentally friendly, (red) demulsifiers.     

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.     

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.     

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.     

Investigation of the Demulsification Efficiency of Some Ethoxylated Polyalkylphenol Formaldehydes Based on Locally Obtained Materials to Resolve Water-in-Oil Emulsions

Fourteen ethoxylated polyalkylphenol formaldehyde surfactants were prepared from locally sourced raw materials. These surfactants were used as demulsifiers to resolve asphltenic crude oil emulsions. Different factors affecting demulsification efficiency such as water:oil ratios, surfactant concentration, surfactant molecular weight, ethylene oxide content, alkyl chain length, and asphaltene content were investigated. From the data obtained it was found that the demulsification efficiency increases by increasing the concentration, alkyl chain length and water content in the emulsion. Also it was found that the increase of asphaltene content in the crude oil impeded the demulsification efficiency. The effect of molecular weight was studied and it was found that the demulsification efficiency was controlled by an optimum range of molecular weight between 3640 to 3810 for the family of demulsifiers studied. Regarding the effect of ethylene oxide content in the demulsifier structure, it was found that the maximum demulsification efficiency was obtaind at 40 units ethylene oxide. The maximum demulsification efficiency was obtained by TND5 (m.wt. = 3800, eo = 40 units). With this demulsifier 100% water separation was exhibited after 35 minutes at 150 ppm demulsifier concentration and 50% w/o emulsion. The surface, interfacial tension, and hydrophilic lipophilic balance (HLB) of the invistigated demulsifers were studied. The obtained results justified that they are strongly related to the demulsification effeciency.     

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.     

Screening and Demulsification Mechanism of Fluorinated Demulsifier Based on Molecular Dynamics Simulation

In order to solve the problem of demulsification difficulties in Liaohe Oilfield, 24 kinds of demulsifiers were screened by using the interface generation energy (IFE) module in the molecular dynamics simulation software Materials Studio to determine the ability of demulsifier molecules to reduce the total energy of the oil–water interface after entering the oil–water interface. Neural network analysis (NNA) and genetic function approximation (GFA) were used as technical means to predict the demulsification effect of the Liaohe crude oil demulsifier. The simulation results show that the SDJ9927 demulsifier with ethylene oxide (EO) and propylene oxide (PO) values of 21 (EO) and 44 (PO) reduced the total energy and interfacial tension of the oil–water interface to the greatest extent, and the interfacial formation energy reached −640.48 Kcal/mol. NNA predicted that the water removal amount of the SDJ9927 demulsifier was 7.21 mL, with an overall error of less than 1.83. GFA predicted that the water removal amount of the SDJ9927 demulsifier was 7.41mL, with an overall error of less than 0.9. The predicted results are consistent with the experimental screening results. SDJ9927 had the highest water removal rate and the best demulsification effect. NNA and GFA had high correlation coefficients, and their R²s were 0.802 and 0.861, respectively. The higher R² was, the more accurate the prediction accuracy was. Finally, the demulsification mechanism of the interfacial film breaking due to the collision of fluorinated polyether demulsifiers was studied. It was found that the carbon–fluorine chain had high surface activity and high stability, which could protect the carbon–carbon bond in the demulsifier molecules to ensure that there was no re-emulsion due to the stirring external force.     

Synthesis and evaluation of some polymeric surfactants for treating crude oil—Part II. Destabilization of naturally occurring water‐in‐oil emulsions by polyalkylphenol formaldehyde amine resins

In the present work, three polymeric surfactants were prepared and used as demulsifiers; polyalkyl phenol formaldehyde monoethanol amine ethoxylate, eo, 136(D1), polyalkyl phenol formaldehyde diethanol amine ethoxylate, eo, 37(D2) and polyalkyl phenol formaldehyde triethanol amine ethoxylate, eo, 21.5(D3). Their demulsification potency in breaking water‐in‐crude oil emulsions was investigated. In this respect, two naturally occurring Egyptian water‐in‐oil (w/o) emulsions, one of them was waxy and the other was asphaltenic, were used in order to study the demulsification power of these compounds. The data revealed that, the resolution of water from waxy crude emulsion was easier than asphaltenic crude emulsion. The demulsification efficiency increases with increasing demulsifier concentration, contact time and temperature. The interfacial tension (IFT) at the crude oil–water interface was measured, it was found that the concentration of demulsifiers required to cause a minimum IFT are always less than these indicating a maximum demulsification efficiency. All the results were discussed in relation to emulsifier chemical structure and crude oil composition. Copyright © 2002 John Wiley & Sons, Ltd.     

STUDY OF DEMULSIFICATION OF WATER-IN-CRUDE OIL EMULSION

Demulsification of water-in-crude oil emulsion was studied at two different salinities, 0.5% and 10% sodium chloride, using five different nonionic surfactants. Equilibrium crude oil-water interfacial tension was measured with drop volume method. Low molecular weight surfactants were found to be completely ineffective as demulsifiers. Three surfactants which were effective demulsifiers, exhibited good interfacial activity, surface adsorption and surface pressure. The performance of the demulsifiers changed with change in salinity of aqueous phase. Surfactants effective as demulsifiers reduced surface tension of water by more than 25 dynes-cm^-1. For a given crude oil-water system, the surfactant which developed surface pressure in excess of 15 dynes-cm^-1 was found to be good demulsifier for that system. Based upon these studies, a physical model of demulsification has been proposed     

Polyoxyethylenated bisphenol-A for breaking water-in-oil emulsions

Polyethylene glycol (PEG) of different molecular weights, namely, 600, 1000 and 4000 g/mol was reacted with bisphenol A to form compounds having different hydrophile–lipophile balances and hence different surface activities. The interfacial tension at the aqueous/benzene interface was determined. It was found that the concentrations of demulsifiers required to cause a minimum interfacial tension are always less than those inducing a maximum demulsification efficiency. The demulsification efficiency of the prepared surfactants in breaking synthetic water in benzene emulsions stabilized by petroleum asphaltenes was evaluated. The data revealed that the demulsification efficiency increases with increasing demulsifier concentration, contact time and hydrophilicity.     

Influence of demulsifiers of different structures on interfacial dilational properties of an oil-water interface containing surface-active fractions from crude oil

The influences of two commercial demulsifiers that have a straight chain and branch chain, respectively, on the dilational viscoelasticity of an oil-water interfacial film containing surface-active fractions from crude oil were investigated. The branch-chain demulsifier AE-121 could efficiently substitute surface-active fractions of different average molecular weights from the oil-water interface, while straight-chain SP-169 could only efficiently substitute those of large average molecular weight. It was apt to form a mix-adsorption layer with surface-active fractions of small average molecular weight. The results showed that the molecular size (or represented by average molecular weights) of the surface-active fractions was an important factor influencing the reciprocity of demulsifiers and surface-active fractions at the oil-water interface. This effect could be well explained by the difference between sizes of surface-active fraction molecules and vacancies between demulsifier molecules at the interface. The results of SDBS also proved this explanation.     

Application of the response surface methodology for modeling demulsification of crude oil emulsion using a demulsifier

The main objective of this research is to determine the capability of four surface-active compounds namely poly(ethylene glycol) distearate, N,N-dimethyldodecylamine N–oxide solution, polyoxyethylene (10) tridecyl ether, and polyethylene glycol sorbitan monooleate as demulsifier agents in breaking water-in-crude oil emulsion through the bottle test method. The influence of temperature, concentration, water content, and pH on demulsification efficiency of the studied demulsifiers was investigated via the response surface methodology (RSM) and the central composite design method (CCD) was applied to design the experiments. The optimum values of input variables to obtain the maximum water separation efficiency were determined based on the developed model by analyze of variance (ANOVA). The R-squared values demonstrate that the developed models could appropriately predict the experimental results of all demulsifier agents.