微波辐射破乳研究进展

综述了微波辐射破乳的有关研究进展。微波辐射是一种有效的破乳手段，与重力沉降、化学、加热等破乳方法相比，能显著地加速稠油体系，含天然表面活性物质、无机盐、固体粒子、三元复合驱剂等乳状液的破乳，提高破乳效果，并且能够提高破乳脱出水的透光率。无机盐与微波辐射两种破乳方式存在加和作用，在极少量的NaCl，MgCl2，caCl2，KCl存在时，用微波辐射120～150s，破乳率可达100％。微波辐射破乳作为一种很有吸引力的破乳方法已在实验室和油田现场取得成功。     

Stability and demulsification of emulsions stabilized by asphaltenes or resins

Experimental data are presented to show the influence of asphaltenes and resins on the stability and demulsification of emulsions. It was found that emulsion stability was related to the concentrations of the asphaltene and resin in the crude oil, and the state of dispersion of the asphaltenes and resins (molecular vs colloidal) was critical to the strength or rigidity of interfacial films and hence to the stability of the emulsions. Based on this research, a possible emulsion minimization approach in refineries, which can be implemented utilizing microwave radiation, is also suggested. Comparing with conventional heating, microwave radiation can enhance the demulsification rate by an order of magnitude. The demulsification efficiency reaches 100% in a very short time under microwave radiation.     

Demulsification of Solids‐Stabilized Emulsions Under Microwave Radiation

Experimental data are presented to show the influence of solid particles on demulsification. It was found that the solid particles could effectively resist demulsification. Compared with conventional heating, microwave radiation can enhance the demulsification rate by an order of magnitude and increase the demulsification effectiveness. The demulsification effectiveness of the emulsions stabilized by graphite powder can reach 82%–89% in a very short time under microwave radiation, whilst that of the emulsions stabilized by barium sulfate can attain 100% under similar conditions.     

Polymeric Surfactants and Emerging Alternatives used in the Demulsification of Produced Water: A Review

Stable emulsions are frequently encountered in oil production and cause a series of environmental and operational issues. Chemical demulsification is widely used for the separation of oil from water or removal of water from oil. The chemicals used in the demulsification process have a strong affinity to the oil-water interface. This review presents the various types of chemical demulsifiers used for the demulsification of water-in-oil and oil-in-water emulsions. The review covers the relevant properties of polymeric surfactants such as polyether, dendrimers, and natural biodegradable polymeric surfactants. In addition, emerging alternatives like nanoparticles-based demulsifiers and ionic liquids are also reviewed. The factors affecting the demulsification efficiency of these demulsifiers and structure-property relationships are discussed. Copolymers with high hydrophilic content and molecular weight are more efficient demulsifiers. Similarly, the position isomerism (same carbon skeleton and functional groups but a different location of functional groups) strongly affects the HLB and demulsification performance. Generally, dendrimers show better performance compared to linear polymeric surfactants due to their relatively higher interfacial activity, better penetrability, and a larger number of reactive terminal groups. Techniques used to evaluate the performance of demulsifiers are also covered. The review also highlights the current developments and future prospects of chemical demulsifiers.     

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.     

Demulsification Efficiency of Some New Demulsifiers Based on 1,3,5-Triethanolhexahydro-1,3,5-triazine

This study mainly concentrates on the synthesis of three novel demulsifiers and the investigation of their demulsification efficiency. The demulsifiers were derived from 1,3,5-triethanolhexahydro-1,3,5-triazine, which was prepared by the reaction of monoethanol amine with formaldehyde. The 1,3,5-triethanolhexahydro-1,3,5-triazine was ethoxylated by introducing 20 units of ethylene oxide and then esterified at different molar ratios with oleic acid (1, 2, and 3) to give three demulsifiers, namely, E₂₀TO, E₂₀TO₂, and E₂₀TO₃. The chemical structures of the prepared demulsifiers were confirmed by ¹H NMR and FTIR spectrum. The demulsification efficiency of these demulsifiers was tested on the natural water-in-oil (w/o) emulsions (50% water content). From the obtained results, it has been found that the investigated demulsifiers have a great potential to break the w/o emulsions. The trioleat ester (E₂₀TO₃) exhibited the maximum demulsification efficiency (96%) after 120 minutes at 55°C.     

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.     

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.     

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.     

Polyoxyalkylenated amines for breaking water-in-oil emulsions: effect of structural variations on the demulsification efficiency

In the present work, different aliphatic and aromatic amines were ethoxylated after a previous propoxylation (PPPEA) with different degrees of propoxylation and ethoxylation in order to obtain polymeric surfactants having different hydrophilic–lipophilic balance (HLB) values. The influence of the structural variations in the prepared PPPEA on their efficiency as demulsifiers for water-in-oil emulsions was investigated. Synthetic water-in-benzene emulsions stabilized by petroleum asphaltenes was utilized for the completion of this study. The actual propylene oxide (PO)–ethylene oxide (EO) ratios of the PPPEA under investigation was elucidated via ¹H NMR spectroscopy. It was found that each demulsifier practices a maximum demulsification efficiency at an optimum concentration. At this concentration, the demulsifiers’ molecules were believed to form a monolayer by adsorbance at the benzene–water interface. The influences of the number of aromatic rings in the molecule, the degree of substitution in the aromatic rings, the number of amine groups, the number of PO–EO chains and HLB on the demulsification efficiency were accomplished. © 1998 John Wiley & Sons, Ltd.     

Chemical demulsification of natural petroleum emulsions of Assam (India)

About one third petroleum production of every oil field is in the form of water in oil emulsions which are normally stabilized by the nickel and vanadium porphyrins from asphaltene portion of crude. The petroleum emulsions of Assam oil fields which have been taken for the present work, are stabilized by the organometallic compounds of iron and high molecular weight compounds from asphaltenes. There is least possibility of any change on these natural petroleum emulsions. The Assam oil field emulsions have been tried to be broken by polyoxyethylene alkyl phenols, their sulphonates and sodium sulphonates in different combinations. The nonyl and octyl phenols with 30 and 40 molecules of ethylene oxide are found most suitable demulsifiers for Lakwa, Rudrasagar and Galeki (Assam) oil fields emulsions. The effect of polyoxyethylene alkyl phenols followed by the treatment of polyvalent cations had been studied for the first time in the field of demulsification of natural petroleum emulsions. This new combination has shown the best results as this broke even the most stable petroleum emulsions which could not be broken by polyoxyethylene alkyl phenols alone. In the present paper a simple method for calculating the chemical demulsification efficiency and a factor H/S paralleled to HLB & H/L for evaluating the emulsification property of surface active agents, have been introduced.     

Synthesis and Evaluation of New Demulsifiers Incorporating Linear Alkyl Benzene Moiety for Treating Water-in-Oil Emulsion

In the present study, five types of water soluble demulsifiers based on linear alkyl benzene were prepared. The chemical structures of the prepared demulsifiers were elucidated using Fourier transform-infrared (FTIR) and ¹H NMR spectra. Different factors affecting demulsification efficiency such as; water content, demulsifier concentration, hydrophilic lipophilic balance (HLB), and ethylene oxide unit were investigated. Also, the rheological properties in relation to demulsification efficiency were studied. The surface and thermodynamic parameters of the prepared demulsifiers were determined at 25°C including, surface tension (γ) and effectiveness, maximum surface excess (Γ_max), and minimum surface area (A_min). From the obtained data, it was found that the demulsification efficiency increases with increasing the water content and concentration of the demulsifiers. Primarily evaluation study of demulsification performance of the new demulsifiers showed that as the ethylene oxide unit in the demulsifiers increase (10–40 ethylene oxide units), the performance of the demulsifiers increasing, however, it decrease in case of demulsifiers with (80 ethylene oxide unit).     

New Amphiphilic Ionic Liquids for the Demulsification of Water-in-Heavy Crude Oil Emulsion

This work aimed to use abietic acid (AA), as a widely available natural product, as a precursor for the synthesis of two new amphiphilic ionic liquids (AILs) and apply them as effective demulsifiers for water-in-crude oil (W/O) emulsions. AA was esterified using tetraethylene glycol (TEG) in the presence of p-toluene sulfonic acid (PTSA) as a catalyst obtaining the corresponding ester (AATG). AATG was reacted with 1-vinylimidazole (VIM) throughout the Diels–Alder reaction, forming the corresponding adduct (ATI). Following this, ATI was quaternized using alkyl iodides, ethyl iodide (EI), and hexyl iodide (HI) to obtain the corresponding AILs, ATEI-IL, and ATHI-IL, respectively. The chemical structure, surface activity, thermal stability, and relative solubility number (RSN) were investigated using different techniques. The efficiency of ATEI-IL and ATHI-IL to demulsify W/O emulsions in different crude oil: brine volumetric ratios were evaluated. ATEI-IL and ATHI-IL achieved promising results as demulsifiers. Their demulsification efficiency increased as the brine ratios decreased where their efficiency reached 100% at the crude oil: brine ratio (90:10), even at low concentrations.     

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。     

Demulsification of Heavy Oil-in-Water Emulsion by a Novel Janus Graphene Oxide Nanosheet: Experiments and Molecular Dynamic Simulations

Various nanoparticles have been applied as chemical demulsifiers to separate the crude-oil-in-water emulsion in the petroleum industry, including graphene oxide (GO). In this study, the Janus amphiphilic graphene oxide (JGO) was prepared by asymmetrical chemical modification on one side of the GO surface with n-octylamine. The JGO structure was verified by Fourier-transform infrared spectra (FTIR), transmission electron microscopy (TEM), and contact angle measurements. Compared with GO, JGO showed a superior ability to break the heavy oil-in-water emulsion with a demulsification efficiency reaching up to 98.25% at the optimal concentration (40 mg/L). The effects of pH and temperature on the JGO’s demulsification efficiency were also investigated. Based on the results of interfacial dilatational rheology measurement and molecular dynamic simulation, it was speculated that the intensive interaction between JGO and asphaltenes should be responsible for the excellent demulsification performance of JGO. This work not only provided a potential high-performance demulsifier for the separation of crude-oil-in-water emulsion, but also proposed novel insights to the mechanism of GO-based demulsifiers.     

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。     

Synthesis and Preliminary Demulsification Efficiency Evaluation of New Demulsifiers Based on Fatty Oils

Three raw fatty oils were used as precursors for demulsifiers. The hydrolyzed form of each oil was adducted with maleic anhydride then modified by esterification with polyethylene glycols or ethyleneoxide-propyleneoxide block copolymers. The demulsfication efficiency, coalescence rate, some surface active, thermodynamic properties, and partition coefficient of a selected demulsifier were investigated. The best demulsifier shows 100% demulsification after 19 minutes at 300 ppm. A correlation between demulsification efficiency and rheological properties of the investigated demulsifier was investigated. Also, emulsification kinetics were followed by microscopic photography. A mechanism following coalescence and flocculation of water droplets is proposed.     

Compressibilities and excess surface areas of mixed asphaltene/resin monolayers. Influence of demulsifiers.

Compressibilities (C_s) and excess surface areas (ΔA_M) are calculated for mixed films of asphaltenes and resins and asphaltenes combined with different commercial demulsifiers from Langmuir measurements. Both attraction and repulsion is observed between asphaltenes and resins, depending on the composition of the film. High molecular weight demulsifiers present in an asphaltene film increase the compressibility and the repulsion in the film, which is important for the demulsification process of water and crude oil emulsions.     

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.     

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