高效原油破乳剂GE-189的制备与应用研究

以分子量大、活泼氢多、具有分支结构的瓜胶作起始剂，与环氧乙烷、环氧丙烷加成，首次合成出具有分支结构的瓜胶类原油破乳剂GE－189，并把这种破乳剂及其与常规破乳剂F3111的复配体系应用于不同油田原油乳状液的室内破乳脱水试验。结果表明，破乳剂复配体系在脱水速率、脱水效果等方面均优于各现场剂，把这种破乳剂与生物表面活性剂复配，于巴西海上油田原油乳状液的破乳脱水，能够显著提高原油乳状液的破乳脱水速率和脱水体积，两者之间表现出明显的协同作用。     

多元复合原油破乳剂的研究和应用

本文评价了几种破乳剂对克拉玛依原油的破乳效果。进行了单剂和复配剂的化学破乳及除油率的筛选。结果表明复配破乳剂在加药浓度、净化油含水和净化水含油、脱水速度等方面均优于单剂。表明复配破乳剂是高效原油破乳剂的研究方向之一。     

优秀原油破乳剂所具备的性能初探

原油破乳剂是国内外油田矿场所必需的化学药剂,可在针对性的破乳剂性能选择上一直缺乏系统的理论支持。由于原油组成的复杂性,加上影响形成乳化原油的因素众多,给原油破乳剂的研究工作带来许多困难。本文从原油乳状液的形成机理入手,分析了乳状液的稳定性原因、破乳机理、破乳剂分子结构性能、物化性能与破乳效果,提出了优秀的原油破乳剂所应具备的性能。     

Fe3O4-PEI磁化破乳剂的制备及性能研究

针对乳化原油破乳难度较大的问题,提出了在磁化破乳剂上枝接聚乙烯亚胺（PEI）,增加磁性粒子表面官能团的解决方案,并对其结构进行了表征。研究了破乳剂加量、沉降时间和pH对其破乳效果的影响,磁性粒子的循环利用率,并对其破乳机理进行了探讨。结果表明：磁化破乳剂最优加量为600 mg/L;沉降2 h后,乳化原油透光率仍可达到98.3%;磁化破乳剂Fe₃O₄-PEI在酸性环境中的破乳效果优于碱性环境;磁性粒子重复利用10次后,透光率仍超过90%。      

TA4812和AP442原油破乳剂的复配研究

为了解决陕北油田现用原油破乳剂脱水率低、污水含油和悬浮物多等问题,合成TA4812和AP442两种新破乳剂单剂,并与助剂ECH用不同比例复配,用陕北油田有代表性的河庄坪和子长原油进行脱水实验。结果表明,对河庄坪原油,在55℃,破乳剂总用量100 mg.L-1,脱水时间6 h,TA4812、AP442与ECH复配比例为4:1时,脱水率最高,分别达到96.7%和97.7%;对子长原油,在65℃,破乳剂总用量200 mg.L-1,脱水时间6 h,TA4812与ECH复配比例为4:1、AP442与ECH复配比例为2:3时,脱水率最高,达到98.3%。     

海上含聚稠油深度脱水破乳剂研究

2018年渤海某聚驱稠油油田开始大幅提产,原油流程超负荷运行导致外输原油含水率升高至15%。通过分析原油系统各级分离器乳化液稳定性,确定了深度脱水破乳剂的开发方向。分别以乙二醇、丙二醇和丙三醇为起始剂合成EO-PO-EO型嵌段聚醚破乳剂。室内实验表明,破乳剂A2321能够大幅降低聚驱稠油中的含水率和乳化液含量,其脱水效果明显优于破乳剂AE8051、BP169和SP169。矿场试验结果表明,破乳剂A2321可将外输原油含水率从15%降低至8%,有效解决了电脱水器中乳化液的深度脱水问题。     

微波用于破乳的研究

原油自井下开采出来要穿过窄隙,与水和气混在一起。油中含有沥青质、石油环烷酸;水中含有各种矿物质,都是天然的乳化剂。因此,大量原油将以乳状液的形式被开采出来,大多数为油包水型(W/O),开发到中后期还会出现油包水、水又包油(O/W/O)型。这种原油无法进一步加工,于是,原油脱水成为采油和集输中一个普遍关注的问题。原油脱水国外较多使用化学破乳法,我国各油田多使用电—化学破乳。电—化学脱水法对高含水原油的适应性差,还需增设预脱水工序。而纯化学脱水,试剂昂贵,生产费用较高。因而,近年来人们开始探索将超声技术、微波技术用于破乳。本文考察了微波破乳效果及其机制,并与常规法进行比较。     

十八烷基超支化分子的结构表征与破乳性能

以甲醇为溶剂,用十八胺、丙烯酸甲酯和乙二胺为原料,通过迈克尔加成反应和酰胺化缩合反应,制备了1.0 G超支化分子;通过红外光谱、核磁共振手段对合成产品的结构进行了表征,且考察了十八烷基超支化分子对O/W型原油模拟乳液的破乳性能,并与传统的线性破乳剂SP-169进行了对比.结果表明:在温度为50℃、添加量为20 mg/L、破乳时间为120 min的条件下,其脱水率达到了76.2%,脱出水中的含油量为41.9 mg/L;而破乳剂SP-169在相同的条件下的脱水率为61.5%,脱出水中的含油量为52.4 mg/L.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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     

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.     

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.     

Chemical destabilization of crude oil based emulsions and asphaltene stabilized emulsions

A comparison of low and high molecular weight demulsifiers and their effect on both crude oil and asphaltene based water-in-oil emulsions is performed. Physical characteristics are given for crudes and for the chemicals. These parameters were then correlated with the demulsifier performance. Results indicate that a significant lowering of interfacial tension is required, but not sufficient for an efficient demulsification. Addition of the chemicals directly to the oil phase prior to emulsification, i.e., as inhibitors, increased the performance of the chemicals significantly. Received: 3 May 2000 Accepted: 10 July 2000     

The Application and Research of Dispersing In Situ Nano-SiO2 in Polyether Demulsifier TA1031

In order to enlarge the application range of nanomaterial and improve the demulsification performance of macromolecule polyether demulsifier, the nano-SiO₂ was dispersed in situ in polyether demulsifier TA1031 to form a new high efficiency demulsifier. The new demulsifier was analyzed by FTIR, SEM, rotational viscometer, and interfacial tension meter. The result showed that dispersing nano-SiO₂ in crude oil demulsifier would greatly improve the demulsification performance of the original demulsifier. When the ratio of silicon dioxide and TA1031 is 1:10 (mass ratio), the demulsification performance of the new demulsifier was the best, and the dehydration rate of emulsion increased about by 20%. Also the time of demulification and dehydration would be greatly shortened, and the demusification mechanism was preliminary analyzed.