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Study on demulsifier formulation for treating Malaysian crude oil emulsion
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Water in oil emulsion occurs at many stages in the production and treatment of crude oil. About two third of petroleum production of every oil field exists in the form of water in oil emulsion. The emulsion stability results from the presence of interfacial barrier preventing coalescence of the dispersed water droplets. This is due to the present of polar components such as asphaltenes, resins, wax and naphtenic acids in the crude oil. Therefore before transporting or refining the oil, it is essential to separate the water for economic and operational reasons. Minimizing the water level in the oil reduces pipeline corrosion and maximizes pipeline usage. The most effective method to overcome the problem is to demulsify the crude by using demulsifiers. The demulsifiers will destabilize the interfacial film between the droplets. It has been reported that the combination of oil-soluble demulsifiers and water-soluble demulsifiers produced great result in water separation. From the screening process of single oil-soluble demulsifiers, the most effective chemicals as demulsifier are TOMAC, hexylamine and dioctylamine while methyl methacrylate, butyl acrylate and acrylic acid are the most effective chemicals in water-soluble group. The new formulation of demulsifier was formulated by using Statistical Analysis System software. From this analysis, the optimum concentration needed for TOMAC, hexylamine, dioctylamine, methyl methacrylate, butyl acrylate and acrylic acid are 48.7 ppm, 0 ppm, 8 ppm, 48.2 ppm, 26.5 ppm and 29.9 ppm, respectively. The combination of these chemicals resulted 53.7% to 60.4% water separation from the emulsion system. It was found that this formulation is better than other commercial demulsifier formulation. This new formulation was found to be effective for demulsification of water-in-oil emulsion of Tabu, Seligi, Guntong, Semangkok, Irong Barat and Tapis fields and single emulsion system. In order to obtain better understanding and results, optimizing on agitation and temperature conditions, the mechanism demulsification study are recommended for further study.
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... The effect of pH values, temperature, salinity on the stability of (Kirkuk / baba, Khbbaz) crude oil emulsion have been studied in the present investigation. In addition, the influence of demulsifies ingredients on stability of the emulsion is studied in order to understand the water-in-oil emulsion behavior an experimental data designed and software, used to state an optimized formulation for water separation These experiments were done by bottle test method, which is the most common method for evaluating the amount of water separated from water-in-oil emulsion [18]. ...
... The volume of water separation from the emulsion system was observed. Water separation versus time and demulsifier concentration was plotted[18]. ...
In this study oil-soluble (RP6000 and MAKS-9150) emulsion breakers have been selected for separation of water from Kirkuk / baba (50oC), Khbbaz (40oC) crude oil emulsions and their activity measured using the Bottle test method at different concentration and found the activity of RP6000 demulsified best than MAKS-9150 emulsion breakers. RP6000 separated water (100%) in (15)min., (40)ppm and in (60)min., (20)ppm of demulsified for Kirkuk/ baba Crude oil and for khbbaz Crude oil the (100%) water separation was in (15)min., (80)ppm and in (30)min., (60)ppm and PH effect, salinity, temperature and density of emulsion stability depending on literature were explained for Optimization.
... From figures (2 to 5) it could be observed that values of removal efficiencies increase with increasing dose of frother (caprylic acid), where maximum value obtained at (20 ppm) and (4cm/sec) at the bottom stage (96.3%).From figures(6 to 9) it could be observed that removal efficiency increases with increasing both frother concentration and gas velocity in presence of hexanol, but it was less than in case of using caprylic acid , where only (94.3%) removal efficiency obtained , while (96.3%) for caprylic acid in same operating condition (Cf=20ppm and Vg=4cm/sec).This because caprylic acid has longer branched chain than hexanol, where longer branched chains has a greet solubility with wastewater than short one therefore, caprylic acid has a good ability to promote separation than hexanol.This behavior as same as the behavior obtained by (Abduljabbar ,Shiao, Hanapi and Wan) [9,10,11,13] . Generally, addition of frother up to a certain concentration has produced impact on reducing bubble size , because the interfacial surface tension is reduced. ...
... Most of the researches dealing with the water and oil emulsions and demulsifiers used the bottle test as the main testing method [36] [37], but in this research the spectroil test has been used according to ASTM6728 (Standard Test Method for Determination of Contaminants in Gas Turbine and Diesel Engine Fuel by Rotating Disc Electrode Atomic Emission Spectrometry ) to mimic the demulsification process used in the power plant because many elements used in the oil processing in the power plant do not exist in the bottle test like stirring, washing water and centrifuge. Also the quality test used by the power plants is the spectroil so it's convenient to use the same testing method and by the same testing device. ...
Demulsifiers are very important additives in the oil industry due to their crucial role in solving the water – in – oil emulsions problem. Inventing new demulsifiers have gained a lot of researchers’ attention; factors like efficiency, versatility, cost and safety were taken into consideration when preparing new demulsifiers.Recycling industrial waste materials has many great benefits economically and environmentally and in this research methyl methacrylate has been prepared from the depolymerization of Plexiglas wastes, Plexiglas is the trade name for poly methyl methacrylate sheets. The (DM) which refers to depolymerized methyl methacrylate was purified and tested by using many methods such as boiling point, infrared spectroscopy; refractive index and gas chromatography GC to determine its purity. Then the depolymerized methyl methacrylate was used in an oil demulsifier mixture in treating water in oil emulsions in crude oil and HFO which refers to heavy fuel oil. The crude oil samples were taken from Al – Hilla 2 power plant while the HFO samples were taken from the South Baghdad 2 power plant. In this research, the spectr oil test had been used after treating the crude oil to determine the demulsification process by measuring the Na and K salts concentration.The purity of the DM was 96.4% according to the GC test. The spectroil results showed that when the DM was used in a demulsifier mixture with water miscible chemicals and chemicals with sufficient solubilities like acrylic acid and butyl acrylate the best demulsification results were obtained (when using 30% wash water) for both crude oil and heavy fuel oil (HFO) with a demulsifier concentration ranging from (200 – 300) ppm.
... An undisclosed oilfield in the South China Sea is facing emulsion problem as excess water is injected to the well for the enhanced oil recovery purpose [2,3]. Besides, the neighbouring oilfields operated by a different company are also facing the same problem [4]. Emulsion is formed when oil and water are mixed vigorously in the process of entering perforation in the casing with the presence of huge different in pressure between the reservoir and well head [1]. ...
One of the most challenging issue faced by the oil and gas industry is the formation of crude oil emulsion. The emulsion formation will lead to inconsistency in the production performance, which directly affects the economic growth of the industry. Current, conventional de-emulsification methods such as thermal, demulsifiers, and electrical methods are found ineffective in solving crude oil emulsion problem relativity to expected settling time. Therefore, this research aims to propose ultrasonic wave application method for better separation rate to solve crude oil emulsion problem. The effects of ultrasonic waves are investigated by designed experiment under different operating temperature. The optimum operating conditions are investigated and identified through optimization methods in Design Expert Software. The goals of this research are to achieve maximum water and oil separation and minimize the rag layer thickness. Based on the experiments and results, the best operating condition is at operating temperature of 60°C at 40 μm of ultrasonic frequency of 20 kHz. These parameters were able to provide 73.3% of water separation rate and 20% volume fraction of oil layer after eight hours of bottle test.
Emulsions are thermodynamically unstable systems, since they will separate to reduce the interfacial area between the oil phase and the water phase, as a function of time. As a metastable system, surfactant molecules, amphiphilic polymers or solid particles must be present before a stable emulsion system is formed. These components of an emulsion system are called emulsifiers. The relative balance of the hydrophilic and lipophilic properties of these emulsifiers is known to be the most important parameter dictating the emulsion type, whether an oil-in-water (o/w) or water-in-oil (w/o) emulsion. Irrespective of the emulsion type formed, demulsification is a costly exercise in the oil and gas industry. This chapter describes the fundamental role played by surface active agents (surfactants) as integral components of a chemical demulsifier.
This chapter is divided into eight different sections. The first three sections describes the introduction of drilling fluid in general and drilling fluid types along with the major drilling fluid additives, major problems of drilling fluids (related to the shale swelling and hydration), Solution of shale swelling and hydration (emphasis on the use of surfactants). It also discusses about the classification and synthesis of surfactants that are used in the formulation of drilling fluids and potential application for shale inhibitions. The next three of this chapter discusses about the impact of surfactants on rheology and filtration properties, and the evaluation of shale inhibition characteristics with surfactant which has explained all the techniques involved in characterizing drilling fluids for shale inhibition. The last two sections of this chapter discusses about the field applications, recommendations and challenges of surfactants for shale inhibition.
After the primary and secondary methods of hydrocarbon production, the reservoir depletes and often relies on enhanced oil recovery techniques (EOR, a tertiary method) to reduce the residual oil saturation (Sor) to a minimum value. Amongst many methods, the chemical EOR (cEOR) technique of oil recovery is widely implemented. The cEOR technique aims to optimize mobility ratio and reduce interfacial tension (IFT) and the viscosity of in situ oil. A subclass of cEOR is surfactant flooding which uses the principle of IFT reduction to facilitate additional oil gain. This process incorporates the use of surfactants which promotes favorable wettability and forms in situ oil–water (o/w) emulsions driving the oil towards the producing well. This chapter provides insight into different classes and types of surfactants used in cEOR methods. The discussions on different surfactants are carried out broadly in terms of its effect on IFT, temperature stability, adsorption on rock matrix and effectiveness in saline environments.
Oil and gas recovery from subsurface reservoir formations requires the application of appropriate stimulation and production techniques, aimed at restoring sufficient pressure difference within drilled formations. Proper implementation of surfactants aids in enhanced fluid connectivity of the reservoir at initial stages of well stimulation, as well as maintain long-term hydrocarbon production. Nowadays, it is being considered as an effective alternative to conventional fracturing fluids such as polymers, gels, etc. due to low cost of application, alteration of inter-molecular interactions, and prevention of insoluble residues’ formation. It is evident that the physicochemical attributes of surfactant-based fracturing fluids can be suitably modified through the use of combination of additives such as friction reducers, clay stabilizers, acids, iron-control agents, cross-linking agents, non-emulsifiers, buffers, inhibition agents, gels, and associated gel breakers. The primary objective of this method lies in minimizing the extent of oil-water block near the wellbore matric and develop pore-connectivity in hydrocarbon pay-zones to attain good recovery characteristics. Surfactant fracturing fluids, if injected properly, are capable of reducing flowback, improving fluid stability and effective clean-up. Therefore, it is a possible route for petroleum engineers and fracture design professionals to produce oil and gas from low permeability reservoir zones via hydraulic fracturing technique, whilst attaining maximum recovery efficacy, production rate and economical operation. This chapter provides a detailed description of design and methodology of surfactants as fracturing fluids in the petroleum industry.
Water–in–oil emulsions are a big challenge in the production and processing of crude oil due to its bad influence on the fundamental and practical aspects of industrial facilities. Researches for decades gave this phenomena a great deal in the planning to construct power plants, refineries, oil companies and other industrial facilities that uses crude oil as a raw material. In order to overcome the disadvantages and hazards of water–in–oil emulsions researchers used chemical, electrical, thermal and mechanical methods individually or in combination. The chemical method has gained the main interest due to its ease of use and economic feasibility. Demulsifiers have been used extensively to solve the problem of water in oil emulsions. The choice of using the right combination of chemicals had been reached after studying many factors such as cost and safety. This research addresses many fundamental and practical aspects regarding demulsifiers and oil demulsification aiming to find the best selection of chemicals that can be used to treat crude oil before using, refining or transporting it. The crude oil in this research had been demulsified and tested by the spectroil test method while the bottle test method had not been used to mimic the demulsification process used in power plant. The work was carried out using two types of oil, crude oil (containing 7 ppm Na and K salts concentration) and heavy fuel oil HFO (containing 12 ppm Na and K salts concentration). The crude oil samples were taken from Al – Hilla 2 power plant while the HFO samples were taken from South Baghdad 2 power plant. The results showed that the water miscible chemicals and chemicals with sufficient solubility that used as a demulsifiers like the acrylic derivatives gave the best demulsification when using more wash water percentage. While the combination of water miscible chemicals and chemicals with sufficient solubility and oil soluble chemicals gave the best results in treating heavy fuel oil while using less wash water percentage.
The formations of emulsions by droplet breakup mechanisms is described in relation to the rheological properties of the dispersed and continuous phases. Once emulsions are formed, their stability is largely determined by the molecular, electric double-layer, steric, and hydrodynamic forces. The application of Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory to successfully predict the stability of oil-in-water emulsions is described. The stability of water-in-crude-oil emulsions can be monitored with electrokinetic sonic analysis; the change in size of the water droplets is indicated by the change in the ultrasound vibration potential signal. With this development, the dewatering characteristics of chemical demulsifiers can be assessed rapidly. For water dispersed in conventional crude oil, a combination of oil-soluble and water-soluble demulsifiers gave the best results.
Surfactants(or surface active agents) are special molecules which are made up of two sections: the hydrophilic part (usually ionic or nonionic) which likes water and the hydrophobic part (usually hydrocarbon chain)which likes oil. It is this dual nature which causes these molecules to adsorb at the interfaces between two immiscible liquids, like oil and water. The interfacial layer formed as a result of this is usually a monolayer and is responsible for allowing oil and water mix. These monolayers play an important role in a number of industrial areas involving surfactants, for example, in pharmaceutical, agrochemical and food preparations, in the detergent industry as well as in numerous processes encountered in the oil business. This article discusses these applications.
The stability of emulsions depends on, amongst other factors, the equilibrium phase behaviour in the oil+water+stabilising surfactant system. In high hydrophile-lipophile balance (HLB) systems, where an aqueous micellar solution or an oil-in-water (O/W) microemulsion coexists in equilibrium with excess oil phase, homogenisation produces an O/W (macro)emulsion. Low HLB systems on the other hand, in which a water-in-oil (W/O) microemulsion (or reverse micellar solution) coexists at equilibrium with an excess aqueous phase, produce W/O emulsions on agitation. An effective way to break emulsions is to change the HLB by some means. Here we discuss the resolution of crude oil emulsions by a commercial chemical demulsifier in these terms. We also show how the stability of emulsions (both O/W and W/O) formed from a pure alkane varies with the HLB of the system, which is changed by altering the concentration of inorganic electrolyte (NaCl).
In the emulsion coalescence process in demulsification, the approach of two droplets under the capillary pressure acting normal to the interface, causes liquid to be squeezed out of the film into the bulk. The rate of drainage of the film is strongly dependent upon adsorption kinetics of the demulsifier, its interfacial activity and solubility, and interfacial rheological properties such as interfacial tension gradient or elasticity, and interfacial viscosity. The predictions of our recent theoretical model for the drainage of film in the drop-drop coalescence process are reviewed which indicates that the interfacial activity of the demulsifier, in addition to its partitioning ability, must be high enough to suppress the interfacial tension gradient. This accelerates the rate of film drainage, thus promoting coalescence. Recent experimental data on demulsification of water-in-oil emulsions using oil soluble demulsifiers are presented which verify the predictions of the theoretical model.
The basic principles and practical aspects of experimental design are presented in this paper for the various stages of an R&D investigation. Statistical data analysis techniques that can be applied with the designs are also provided.