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82742812.Pdf View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Elsevier - Publisher Connector Egyptian Journal of Petroleum (2016) 25, 565–574 HOSTED BY Egyptian Petroleum Research Institute Egyptian Journal of Petroleum www.elsevier.com/locate/egyjp www.sciencedirect.com REVIEW Formulation of best-fit hydrophile/lipophile balance-dielectric permittivity demulsifiers for treatment of crude oil emulsions C.M. Ojinnaka a, J.A. Ajienka b, O.J. Abayeh a, L.C. Osuji a, R.U. Duru c,* a Pure & Industrial Chemistry Department, University of Port Harcourt, Nigeria b Petroleum & Gas Engineering Department, University of Port Harcourt, Nigeria c World Bank Africa Centre for Excellence, University of Port Harcourt, Nigeria Received 17 September 2015; revised 27 November 2015; accepted 8 December 2015 Available online 16 January 2016 KEYWORDS Abstract The commerce of crude oil depends heavily on its water and salt contents usually referred Crude oil; to as Basic Sediments and Water (BS&W), which is co-produced with the crude oil in the form of Emulsion; emulsion. The lower the BS&W, the higher the market value of the crude. The presence of water in Demulsifiers; crude oil causes corrosion, lowers capacity utilization of production and processing plant parts and Plant extracts; pipelines, reduces oil recovery and increases the oil content of the effluent water. The stabilizing fac- Screening tors of crude oil emulsions vary from one oil field to the other and with time in the same well as co- produced water increases, or after a well treatment and Enhanced Oil Recovery Operations (EOR). Periodical assessment and possible change of demulsifiers employed is therefore necessary at certain stages of crude oil productions, but this is not encouraged due to lack of general formulation pro- cedures and the rigorous nature of bottle test method that is currently being used for assessment and selection. In this paper, the factors that affect the stability of crude oil emulsions are presented. Efforts of researchers in formulating demulsifiers based on these factors and their screening meth- ods were reviewed. The context sets the stage for further exploration of possible relationship(s) between the physical parameters of the crude oil and the demulsifiers, and exploiting same in the formulation of new demulsifiers capable of resolving crude oil emulsions using chemicals with improved surface activity and crude extracts of indigenous plants. Ó 2016 The Authors. Production and hosting by Elsevier B.V. on behalf of Egyptian Petroleum Research Institute. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/ licenses/by-nc-nd/4.0/). * Corresponding author. Peer review under responsibility of Egyptian Petroleum Research Institute. http://dx.doi.org/10.1016/j.ejpe.2015.12.005 1110-0621 Ó 2016 The Authors. Production and hosting by Elsevier B.V. on behalf of Egyptian Petroleum Research Institute. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). 566 C.M. Ojinnaka et al. Contents 1. Introduction . 566 2. Composition of crude oil . 566 3. Emulsion formation in crude oil production . 567 4. Factors that affect emulsion stability. 568 4.1. Crude oil components . 569 4.2. Addition of diluent . 569 4.3. Temperature and pH. 570 5. Crude oil demulsification . 570 6. Demulsifiers . 571 7. Conclusion . 573 References . 574 1. Introduction branched or cyclic alkanes. The cycloalkanes may have side chains and multiple rings but the distinguishing characteristic In pharmaceutical and cosmetic industries, emulsions are of the saturates is the absence of multiple bonds. Wax (straight desired for formulation stability. In the petroleum industry, chain alkanes with C20–C30 carbon range), one of the compo- emulsion is undesirable, so chemists and engineers seek means nents that contribute to crude oil emulsion stability belongs to of breaking or destabilizing emulsions formed in the process of this saturate fraction [7,8]. producing crude oil from the reservoir. Aromatics are the fraction that contains cyclic compounds An emulsion is a type of colloidal dispersion consisting of whit benzene ring structure. The rings may be one or more two incompletely miscible liquids, one (the dispersed or inter- (fused) with or without side aliphatic substituents. nal phase) being distributed in finite globules in the other [the The resin fraction is somewhat similar to the aromatic but continuous or external phase (1)]. There are two basic types of differs with the possession of higher molar mass and contains emulsion; Oil-in-Water (O/W) and Water-in-Oil (W/O) emul- at least one heteroatom in their ring structure making them to sions. W/O emulsion is formed when water is the dispersed be more polar. Operationally, resins can be defined as the frac- phase and oil is the continuous phase. Conversely, if oil is tion that is soluble in light alkanes such as n-pentane and n- the dispersed phase and water is the continuous phase, it is ter- heptane but insoluble in propane [7,9,10]. med Oil-in-Water emulsion. Water-in-Oil emulsion is the type In the SARA analysis procedure, the asphaltene fraction is that is usually encountered in crude oil production. usually the first to be precipitated out of the crude oil bulk The presence of water in crude oil presents a number of using n-pentane or n-hexane. The structure of asphaltene problems to its production, transportation and processing structure (Fig. 2a) is yet to be well defined but it is generally leading to increased down-time in the petroleum industries. believed to consist of polycyclic aromatic clusters with esti- These problems include [2–6]: mated molecular weight of 500–2000 g/mol [7]. They are the heaviest and most polar fraction of the crude oil with fused (i) Limitation of space in the processing and transporting aromatic rings (more than in resins), aliphatic side chains vessels leading to reduced net efficiency of the vessels. and one or more hetero atoms. As a result, they play the major (ii) Corrosion of production plant parts and pipelines, an role of stabilizing water in oil emulsion [7,10,11]. effect which is further enhanced by the presence of dis- The knowledge about the chemical composition of crude solved salts in the water phase. oils, gained from, for instance a SARA-analysis, cannot fully (iii) Emulsion formation may also lead to reduced oil recov- explain the crude oil behavior with regard to emulsion stabil- ery and consequently, environmental concerns due to ity, asphaltene deposition etc. but it is valuable in other fields appreciable oil content of the effluent water. in the petroleum industry such as reservoir evaluation, migra- (iv) Lowering of API gravity. tion and maturity, degradation processes, processing, and Crude oil 2. Composition of crude oil n-hexane Crude oil contains numerous compounds whose constituent precipitate solution elements are more of carbon and hydrogen in varying propor- tions. For convenience, the compounds have been grouped Maltenes into four broad classes – saturates, aromatics, resins and silica asphaltenes (SARA), using their solubility and polarity param- eters. The separation scheme (Fig. 1) into these classes is called trichloro- methane n-hexane n-hexane SARA analysis [7]. The saturate is the fraction that consists of saturated non Asphaltenes Resins Aromatics Saturates polar compounds that are composed of hydrogen and carbon only. Also known as the paraffins, they may be straight-chain, Figure 1 SARA – separation scheme (Aske, 2002) [7]. Formulation of demulsifiers for treatment of crude oil emulsions 567 EOR [14] or during well treatment operations like matrix acidizing. Crude oil emulsions may intentionally be formed before subsequent demulsification during desalting process or to enhance flow in pipeline transportation [15]. Emulsifiers are surface active agents that have both hydro- philic and lipophilic portions in the same molecule. Some com- ponents of the crude oil act as natural emulsifiers leading to emulsion formation during the production process. The frac- tions of crude oil that have been identified as contributing to formation of W/O emulsion include the asphaltenes, resins and waxes and they can exist in both dissolved and particulate form [16]. It has been observed that resins alone may not yield stable W/O emulsions but by their interaction with the asphaltene molecules, they may enhance or reduce their surface activity [10,17,18]. Mclean and Kilpatrick [17] in particular noted that Figure 2 Hypothetical molecular structures of (a) asphaltene (b) resins help to solubilize the asphaltenes by forming resin- resin (c) naphthenic acid (source: Langevin et al., 2004) [12]. solvated asphaltenic aggregates and at such, tend to reduce the surface activity of the asphaltenes. They concluded that as the resin-to-asphaltene ratio, aromaticity of the resin and environmental effects [9]. The SARA distribution of crude oil the H-bonding between the asphaltene and resin molecules from Osso production platform is shown in Fig. 3 [13]. Aske increase, the asphaltene solubilization increases and conse- (2002) [9] used multivariate regression analysis of near IR quently, their ability to stabilize emulsions decreases. Latter, and IR spectra of crude oils originating from variety of pro- Schorling et al. [19], in their separate investigation also found duction fields to analyze the SARA composition (Table 1). out that high asphaltene-to-solvent ratios increase emulsion stability
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