Malkin 2018

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Process Engineering
Modifying the viscosity of crude heavy oil
by using surfactants and polymer additives
Alexander Ya. Malkin, Kirill Zuev, Marianna P. Arinina, and Valery G Kulichikhin
Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.8b02925 • Publication Date (Web): 08 Oct 2018
Downloaded from http://pubs.acs.org on October 9, 2018
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Page 1 of 45 Energy & Fuels
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Modifying the viscosity of crude heavy oil by using
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surfactants and polymer additives
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17 Alexander Ya. Malkin,* Kirill V. Zuev, Marianna P. Arinina and Valery G. Kulichikhin
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21 A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29
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25 Leninsky prospekt, 119991 Moscow, Russia
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30 ABSTRACT: A systematic study of the influence of surfactant and stabilizing polymer
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33 additives on the rheological properties of heavy oils was carried out. The aim was to
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37 optimize the recipe for the most effective reduction in the oil viscosity. A total of 41
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40 versions of the emulsion were prepared using different protocols. Creation of the
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emulsions with different recipes and modes of mixing led to a regulation of their
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47 morphologies, which determined the rheological properties of the final products. In all
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cases, emulsification resulted in a transformation of the oils from Newtonian behavior to
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54 a viscoplastic medium with a blurred yield stress. Depending on the composition, the
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60 ACS Paragon Plus Environment
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Energy & Fuels Page 2 of 45
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4 yield stress was decreased up to 0.6 Pa and the viscosity at high shear obtained a
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7 value up to 50 mPa·s, which is lower than the viscosity of crude oil by 34 times. The
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11 efficiency of the viscosity reduction increased with decreasing temperature.
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16 KEYWORDS: heavy oil, oil/water emulsions, surfactant, viscosity, viscoplastic behavior,
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19 polymer stabilizer
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1. INTRODUCTION
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27 A reduction in the viscosity of heavy oil during production and transportation is one of
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the key issues in the modern petroleum industry. This issue is related to the increasing
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34 exploitation of heavy oil fields due to the inevitable exhaustion of traditional sources of
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light oil. The general goal is to reduce the viscosity level of the heavy oil to 200 or 400
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41 mPa·s in accordance with the requirements of the technical possibilities of existing
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44 piping lines.1, 2
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48 Crude oil is a very complicated multi-component system with strong dependencies of
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51 its rheological properties on the composition.3-5 Therefore, there are several technical
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55 approaches for reduction of its viscosity.1 One of the most promising concepts is the
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4 formation of oil/water (o/w) emulsions. The formation of emulsions in crude oil is a
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7 spontaneous process related to interaction of asphaltenes with resins and other
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11 components as well as water while oil components are mixing in flow.6-8 Meanwhile the
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14 presence of natural lipophilic stabilizers in crude oil prevents transformation of existing
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18 water/oil (w/o) emulsions into o/w ones.
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21 Such colloidal particles as asphaltenes are inclined to form rather large clusters
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25 similar to those described in the work.9 Hence, their rheological behavior can drastically
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28 differ from the predictions of classical models of disperse systems.10 Creation of large
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32 and structured colloidal particles leads more likely to an increase of the viscosity due to
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35 organizing percolation bonds. Therefore, the engineering goal is to obtain emulsions
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where heavy fractions of heavy oils create dispersed particles in a low viscous aqueous
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42 medium.11-15 This goal was the subject of numerous investigations which were realized
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in industry in Kalimantan (Indonesia) pipeline and Venezuela (Orimulsion® project).11
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49 Compositions which can be used for reduction of the viscosity of heavy oils can be
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called by a general term as viscosity reducers. Very likely, all of them promote formation
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56 of the o/w emulsions. The creation of o/w emulsion is by essence, a decrease in
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4 interface tension using surfactant with high hydrophilic-lipophilic balance (HLB). This
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7 result is reached by addition of a wide set of liquid surfactants of very different type
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11 including polymeric compounds.16 Possibly, a promising way consists in modification of
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14 natural components (asphaltenes and others) to transform crude oil into o/w emulsions
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18 as well as using mineral micro-/nanoparticles containing in crude oil for formation of the
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21 Pickering emulsions.12, 17 Solid colloidal particles concentrated at interface layers allow
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25 for creation stable emulsions.18-20 A rather peculiar method for producing o/w emulsions
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28 is using bio-objects as surfactants.21
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32 Using surfactant mixtures especially including polymers is of special interest in
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35 improving the rheological properties of oils. Light scattering study showed that an
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addition of macromolecules influences the size of dispersed particles and formation of
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42 micelles.22, 23 Typical example of such composition is a mixture of polymeric compounds
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and Triton-X100.24 Recently, a new amphiphilic oil-soluble quadripolar copolymer (on
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49 the base of 2-(acrylamide)octane sulfonic acid) was proposed for destruction large high-
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molecular components in crude heavy oil.25 It seems reasonable to consider this
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56 compound as a peculiar surfactant.
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4 Meanwhile, most likely, there is no universal optimal recipe and it is necessary to
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7 search for special viscosity reducer and stabilizing systems for any the new crude heavy
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11 oil grade. The preliminary selection of surfactant (or modifying system) is based on the
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14 rheological properties of interfacial levels26, 27 as well as direct structure methods, e.g.
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18 small-angle neutron scattering for studying surfactant micelles.28 Different versions for
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21 emulsifying systems were considered in many publications including experimental
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25 studies of model systems and real oils. Generally speaking, the role of the surfactant is
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28 to reduce the interfacial tension between the oil and the water and as a result to modify
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32 the flow properties.29, 30
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35 The next important point for technological applications of oil/water emulsions is their
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stability. This is a twin-side story. First, emulsions should be stable enough for oil
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42 transportation but emulsions should be destroyed at entering the stage of oil treatment.
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Therefore, stability of emulsions and the choice of the reliable methods are of special
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49 importance.31
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Emulsification of heavy crude oil with formation of o/w emulsions as an effective
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56 method for reduction of its viscosity was experienced in our previous work and the
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4 surfactant choice and formation of the definite emulsion morphology were stressed as
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7 determining factors.32, 33 In this paper, continuing these studies, we present the results
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11 of experiments involving a wide spectrum of surfactants and stabilizing polymer
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14 additives as the base for choosing an optimal composition to provide the rheological
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18 properties and stability of heavy oil-based emulsions.
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25 2. MATERIALS AND METHODS
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28 2.1. Heavy oil. Industrial species of heavy crude oil from Yareg oil field (Ukhta, Komi
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32 region, Russia) were used as the base object for this study. For this oil, the density was
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35 0.944 g/cm3 at 20°C and the API gravity was 19.5. This oil contains a low amount of
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asphaltenes, which did not exceed 3% according to the standard method of hexane
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42 precipitation. The composition of the maltene part of the oil was determined by gas
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chromatography-mass spectrometry (GC/MS, Figure 1) and is presented in Table 1.
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49 The rheological properties of the oil samples were characterized by Newtonian
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viscosity without any clear non-Newtonian effects that are typical for heavy oils.4 The
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56 viscosity was equal to 1700 mPa·s at 25°C. Figure 2 shows that the viscosity sharply
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4 increased as the temperature decreased. The upper limit of the viscosity that is
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7 acceptable for existing tube transport lines is not higher that 200 or 400 mPa·s.2 This
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11 value is several times lower than the viscosity at 25°C, not considering lower
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14 temperatures. The corresponding viscosity levels are shown in Figure 2. This reason
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18 compels the development of methods for viscosity reduction. Furthermore, it is desirable
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21 to have an acceptable level of viscosity at the minimal possible temperature.
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25 2.2. Surfactants. The choice of surfactants for this study was dictated by a
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28 consideration of their nature and their commercial availability because application of the
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32 process in real engineering applications was the goal. For the experiments, nine
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35 surfactants and five polymer modifiers in different combinations enabled control of the
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rheological properties and morphologies of the emulsions. The list of resulting
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42 compounds, their trademarks, chemical structure, and main physical characteristics are
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given in Supporting Information. Among them, various types of water- and oil-soluble
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49 surfactants: anionic (sodium salts of linear alkyl sulfate, alkyl sulfosuccinate and alkyl
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carboxylate); nonionic (based on polyoxyethylene, ethoxylated fatty alcohols and alkyl
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4 phenols, glycols); polyelectrolytes (acrylic acid esters and amides, polyvinyl alcohol,
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7 gelatin, cellulose derivatives) were used.
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11 2.3. Protocols for preparing the oil emulsions. The designations, components, and
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14 peculiarities of preparing the emulsions used in this work are listed in Supporting
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18 Information. The analytical methods used for characterization of all prepared emulsions
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21 are also included in this file.
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25 A basic protocol was developed. The heavy oil samples were emulsified in water in
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28 the presence of surfactants at room temperature (22±2°C) using an Ultra-Turrax T10
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32 mechanical rotor disperser (IKA, Germany). The dispersing operation was done for no
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35 longer than 2 min and usually at low speed (8000 min-1). This operation eliminated
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coalescence and an increase in the viscosity over time. In some cases, a magnetic
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42 stirrer Hei-Tec (Heidolph, Germany) was used.
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Emulsions that used water-soluble surfactants were prepared from their solutions in
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49 distilled water. Oil-soluble surfactants were introduced into the oil/water mixture just
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before the dispersing operation (in some cases, this required to increase temperature).
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4 It was found that separation of the excess quantity of water took place upon
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7 increasing the water-to-oil ratio above 1/3 (25 vol% of an aqueous phase in a mixture),
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11 but the significant increase in the viscosity of the mixtures happened below this ratio.
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14 The stable oil emulsions containing more than 25 vol% of an aqueous phase were
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18 obtained by addition of water-soluble polymers (polyvinyl alcohol, PVA, or hydroxyethyl
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21 cellulose, HEC). These emulsions were obtained at a temperature of 60°C using a two-
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25 step procedure that involved introducing an aqueous phase into an emulsion.
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28 2.4. The morphology of the emulsions. The structure and type of emulsions was
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32 established by differential scanning calorimetry (DSC) using a MDSC 2920 model (TA
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35 Instruments, USA) in the following mode. The sample was cooled from 20°C to -60°C
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with subsequent heating from -60°C to 30°C at the rate of 2 K/min. As seen in work,34
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42 the position of the exothermal peaks permitted the estimation of the water in emulsions
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as either a dispersed phase or continuous medium. The morphology of the emulsions
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49 was observed by preparing thin layers and observing them at high magnification with a
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6PO optical microscope (Biomed, Russia).
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4 2.5. Interface tension measurements. The surface properties of the surfactants,
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7 namely the interface tension at the boundaries of the surfactant/air and surfactant/oil,
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11 were measured. The experiments were performed by the Wilhelmy plate standard
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14 method using a K20 tensiometer (Krüss, Germany) at a temperature of 21±1°С.
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18 2.6. Rheology (viscosity measurements). The rheological property measurements for
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21 the oil and emulsions were carried out at 25°C on the Physica MCR301 rotational
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25 rheometer (Anton Paar, Austria) using the both smooth and rough cone-and-plate pair.
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28 This allowed us to be sure that the wall slip is negligible in the flow curves discussed
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32 below. The pair had a diameter of 20 mm and angle between cone and plate equal to
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35 2°. Measurements in a wider temperature range, from 0°C to 40°C, were carried out
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using coaxial cylinders with the ratio of the cylinder radii equal to 1.084 and the gap
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42 between the cylinders of 0.421 mm. The data obtained using the Couette geometry are
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equivalent with data obtained using the cone-and-plate technique in domains of the
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49 same shear rates.
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3. RESULTS AND DISCUSSION
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4 3.1 Structure of emulsions. A typical thermogram pattern for oil/water and water/oil
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7 emulsions for the samples containing 25 vol% of aqueous solution of surfactant are
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11 shown in Figure 3. As a rule, all water-soluble surfactants provided formation of a
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14 double emulsion (of the water/oil/water type). For such emulsions, two peaks in the
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18 cooling mode were observed (Figure 3(a)), namely a strongly expressed exo-peak
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21 corresponding to crystallization of a continuous aqueous phase (containing solved
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25 surfactant and possible impurities) near -17°C and a weak exo-peak responsible for
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28 water crystallization in the oil droplets. In the heating mode, a single endo-peak near
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32 0°C was observed.
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35 It is worth mentioning that using surfactants with high HLB adding to crude heavy oil
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which initially contained natural lipophilic surfactant in many cases, results in formation
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42 of multiple o/w/o or w/o/w emulsions.35 The w/o/w type emulsions contain rather large
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drops of oil in a continuous aqueous phase, the latter in its turn, include small oil
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49 droplets. Such double-type emulsions compromise rather small share of water (that is
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economically reasonable) and can be the most favorable for the viscosity reduction.
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4 The use of oil-soluble surfactants (for example, Eumulgin O-2 and Eumulgin Prisma)
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7 and water solutions of polymers (Rheovis TTA, Rheovis CSP and Sokalan CP10S)
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11 resulted in the formation of water/oil emulsions. Only one exo-peak (Figure 3(b)) near -
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14 43°C in the cooling mode corresponded to the aqueous droplets crystallization. An
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18 endo-peak in the heating mode near 0°C for water liquefaction was observed.
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21 Typical photomicrographs illustrating the structure of different emulsions are
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25 presented in Figure 4. Photomicrographs of oil/water emulsions ST4 and X2 (Figure
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28 4(a)-(f)) clearly demonstrate a high degree of polydispersity of the droplet sizes and a
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32 resulting high packing density. This may explain the stability of these emulsions in spite
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35 of their large size (about 100 µm for the biggest droplets). A complicated morphology,
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such as double emulsions where small water droplets are inside oil droplets, is also
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42 seen in some of these photos.
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Photomicrographs for water/oil emulsions Eu4 and G1 (Figure 4(g)-(l)) show the
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49 formation of polydisperse aqueous droplets dispersed in the oil phase. In some cases,
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isolated anizometric agglomerates were created.
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4 The intensity of the emulsification was a key factor for determining the size of the
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7 emulsions in the final products and their resulting stability and viscosity.36, 37 It has been
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11 shown (Figure 5(c)) that emulsification that is excessively intense leads to the formation
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14 of emulsions with droplets that are very small and increase both the viscosity and yield
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18 stress. Figures 5(a) and 5(b) shows photomicrographs of emulsions of the same
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21 composition that received different emulsification conditions, namely intensive (sample
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25 X2) and a low-rate emulsification (sample X4). Double emulsions (w/o/w) were obtained
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28 in both cases. However, the share of large droplets appeared to be quite different. This
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32 resulted in the loss of stability of emulsion X4.
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35 The role of the surfactant is to reduce the interfacial tension between the oil and the
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water and as a result to modify the flow properties. Also, the interface tension
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42 determines the compatibility of the components. The surface property measurement
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results are shown in Table 2. The lowest values of the interface tension were found for
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49 the solution of nonionic surfactants Triton X-114 and OP-7, and the highest values were
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obtained for the aqueous solution of polymers Rheovis CSP and Sokalan CP10S. The
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56 values of the interface tension for mixtures of different surfactants are additive.
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4 As a matter of practice, it was observed that the aqueous phase containing the
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7 surfactant with a low surface tension was easily mixed with oil, even when mixed by a
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11 glass rod (Figure 6(a)). The aqueous phase containing surfactant with a high surface
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14 tension could not be homogenized with oil under the same conditions (Figure 6(b)). The
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18 majority of the emulsions under study that were obtained in the presence of an aqueous
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21 polymer solution had poor stability even after high intensity mixing.
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25 3.2. Rheological properties of emulsions. As mentioned above, heavy oil is a
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28 Newtonian liquid. The formation of an emulsion leads to uncertainty in the rheology and
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32 the appearance of a viscoplastic medium, as described in previous work.32 Existence of
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35 a yield stress in concentrated emulsions is a general feature of their rheological
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properties.38, 39 The obtained emulsions can be classified into three groups – unstable
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42 mixtures, water/oil emulsions, and oil/water emulsions with a different morphology. The
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first two groups of emulsions are not of practical value because the viscosity of w/o
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49 emulsions is higher than the viscosity of oil. Thus, only o/w emulsions will be considered
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below. Typical results for the series of emulsions with nonionic and anionic surfactants
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4 A blurred transition through the yield stress with a ten-fold decrease in viscosity at
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7 high shear stresses (in comparison with crude oil) can be observed (Figure 7(a)). Thus,
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11 the level of the apparent viscosity necessary for transportation conditions is reached at
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14 high shear rates. The nature of the surfactant impacts the value of the yield stress (i.e.
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18 the strength of the emulsion structure) but not the apparent viscosity at high shear
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21 stresses. The most interesting sample in the series shown in this figure for governing
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25 the rheology of emulsions is Triton X-114 (designation X2) because it provided the
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28 lowest value of the yield stress. It is interesting to note that Triton X-100 (which is similar
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32 to Triton X-114) is also one of the most effective surfactants for the viscosity reduction.40
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35 Similar effect is provided by the other non-ionic surfactants.41 Usually, one can expect
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that anionic surfactant might be preferable in reducing the o/w interfacial tension and
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42 size of dispersed droplets. Meanwhile decreasing the droplet size is not favorable for
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the viscosity reduction because the viscosity of emulsions with smaller droplets is higher
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49 than with bigger droplets.37 This effect is also shown in Figure 5(c).
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Bearing in mind these considerations, we can expect a positive influence of mixtures
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56 of anionic and non-ionic surfactants for the formation of o/w emulsions and reduction of
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4 the crude oil viscosity. Indeed such an approach allowed for reaching a synergetic
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7 effect. Figure 7(b) shows the flow curves for the emulsions obtained with the anionic
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11 surfactants (SLES), nonionic surfactants (Tween 80), and their mixture. In this case,
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14 both the viscosity and yield stress are lower than values found for the individual
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18 components. The synergetic effect does not always occur; but in some cases, a
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21 decrease in the yield stress is quite noticeable (Figure 7(c)). Mixing of several
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25 components for creating stable o/w emulsions can lead to better results possibly, due to
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28 the self-assembling of the components especially in when using ionic and non-ionic
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32 compounds.42, 43
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35 Changes in the rheology of the emulsions are related to a transformation of their
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morphology and are determined by the nature of the surfactant used or their mixture.
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42 For example, an aqueous solution of nonionic surfactant OP-7 created emulsions with
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droplets of extremely small size (OP1). However, mixtures of OP-7 with anionic SLES
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49 led to the formation of emulsions with droplets of medium size (SOP1), as shown in
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Figure 8(a)-(c). An analogous situation took place when using mixtures of SLES
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56 (sample S1) with nonionic Tween 80 because this resulted in the formation of medium
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4 size droplets as compared to droplets created in the presence of the individual
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7 surfactants (Figure 8(d)-(f)). Thus, varying the compositions of the surfactant mixtures
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11 regulated the droplet size in a dispersed phase and the resulting viscosity and flow
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14 character of the oil emulsions.
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18 The experimental data discussed above were obtained at the same aqueous phase
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21 content (25 vol%) in the emulsions. Meanwhile, understanding the role of the water is
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25 worth special consideration. Thus, the rheological properties of emulsions were carried
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28 out by varying the share of the aqueous phase in the range from 10 to 50 vol%. This
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32 was done with surfactants that demonstrated the strongest influence on the viscosity of
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35 the emulsions, namely Triton X-114, SLES and Tween 80 mixture (with components in
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the ratio 1:1), and PVA.
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42 Mixtures with share of water more that 25-30 vol% appeared unstable and the excess
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quantity of water separated. Mixtures with only 25 vol% of water formed stable oil/water
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49 emulsions. One can suppose that the instability of the mixtures with a higher water
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concentration was due to either the low viscosity of the continuous aqueous phase that
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56 promoted diffusion and coalescence of the oil droplets or creation of an interfacial
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4 barrier of insufficient strength by the surfactants. Both factors can be overcome by the
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7 addition of polymer compounds having sufficient surface activity. Thus, two water-
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11 soluble polymers, namely polyvinyl alcohol (PVA) and hydroxyethyl cellulose (HEC),
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14 were evaluated. Preliminary experiments showed that HEC provided a stronger
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18 thickening effect at much lower concentration than PVA because 0.5 wt% of HEC led to
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21 the same increase in viscosity as 5 wt% of PVA. The addition of the polymers resulted
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24
25 in a significant increase in the stability of the emulsions. It is also important that the
26
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28 viscosity of emulsion ST15, with 50 vol% of aqueous solution of the surfactant mixture
29
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32 and stabilized by HEC, was much lower than the viscosity of the other compositions.
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35 Figure 9(a) presents the experimental data for the rheological properties for a series of
36
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39
emulsions stabilized with either PVA or HEC. If individual surfactants were used, the
40
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42 maximal effect of the viscosity decrease was reached with Triton X-114 and HEC as the
43
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46
stabilizing agent.
47
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49 It was noted43 that emulsification at increased temperature and/or stepwise addition of
50
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53
components positively impacted the stability and other characteristics of emulsions. In
54
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56 this case, this is explained by a decrease of the oil viscosity that promoted distribution in
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18
1
2
3
4 the aqueous phase. The combined effect of temperature and addition of stabilizing HEC
5
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7 (0.25 wt%) is seen in Table 2, where the surface tension for air/aqueous solutions of
8
9
10
11 Triton X-114 are presented for 20°C (without HEC) and 60°C (with HEC).
12
13
14 Emulsions with 50 vol% of water obtained after preliminary heated (up to 60°C) oil and
15
16
17
18 stepwise addition of aqueous solution of HEC and 5 wt% of Triton X-114 appeared quite
19
20
21 stable (see Figure 9(c)). Their rheological properties are presented in Figure 9(b). As
22
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25 seen, addition of the polymer into the emulsion resulted in a rather strong effect of
26
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28 structuring, which was absent in emulsion Х6 (without HEC). Finally, the viscosity of this
29
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32 sample was minimal and remained practically constant for a wide range of shear rates.
33
34
35 It is also interesting to note that addition of HEC (in combination with the increase in the
36
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39
emulsification temperature) promotes formation of emulsions with simple morphology
40
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42 (without any inclusion of water droplets in oil droplets, see Supporting Information).
43
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46
The examination of a series of samples with a different concentration of aqueous
47
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49 phase (samples X5, X8, X9, X10, and X11 with share of water equal to 50, 40, 30, 20
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53
and 10 vol%, respectively) along with 0.25 wt% of HEC as a stabilizing agent gives the
54
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56 results presented in Figure 10 (for 0, 25 and 40°C). It is worth noting that the phase
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19
1
2
3
4 inversion took place in emulsions with 10 vol % of water. This was confirmed for two
5
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7 surfactant mixtures (see Supporting Information). Therefore, the flow curves of the X11
8
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11 emulsion are not shown in Figure 10.
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14 It is worth mentioning that the effect of emulsification grows significantly (up to 170
15
16
17
18 times in comparison with crude oil) for a decreasing temperature (Figure 10(a)). As an
19
20
21 example, the minimal apparent viscosity of emulsions X5 (50 vol% of water) at 0°С
22
23
24
25 appears to be three times lower than the viscosity of crude oil at 40°C. At high
26
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28 temperatures, the apparent viscosity of emulsions only weakly depended of the water
29
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31
32 concentration (Figure 10(c)).
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34
35 For practically all oil/water emulsions studied in this work, their apparent viscosity at
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39
high shear stresses was below the technological limit of 400 mPa·s. In many cases, it
40
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42 was below 200 mPa·s, regardless of the type of surfactant, water concentration, and
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46
method of emulsification.
47
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49 4. CONCLUSIONS
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53
This study of the influence of the surfactant nature, composition, and conditions of
54
55
56 emulsification showed that emulsification radically changes the rheological properties of
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20
1
2
3
4 crude oil. The transition from Newtonian behavior typical for heavy oils to the
5
6
7 viscoplastic flows inherent for concentrated emulsions took place.
8
9
10
11 The intensity of mixing the components should be optimal for obtaining droplets of the
12
13
14 necessary size. The size should not be very large to prevent coalescence and phase
15
16
17
18 separation and not too small to prevent a significant increase in viscosity. Emulsification
19
20
21 at a high temperature (60°C) promoted oil distribution in an aqueous phase and
22
23
24
25 enhanced the stability of the emulsions.
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28 For the compositions under study (chosen oil and surfactants), the maximum volume
29
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32 share of an aqueous phase was 25%. Obtaining emulsions with a higher concentration
33
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35 of water was possible by using polymer stabilizers, e.g. hydroxyethyl cellulose as 0.25
36
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39
wt% water solution, which only slightly increased the viscosity.
40
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42 A transition from crude oil to emulsions impacted the appearance and the level of the
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46
yield stress. However, the apparent viscosity of emulsions at high shear rates (> 1000 s-
47
48
49 1) changed in a narrow range. For emulsions containing 25 vol% of water, the minimum
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53
value of the apparent viscosity (170 mPa·s at 25°C) was reached by using nonionic
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56 surfactants (Triton X-114, Tween 80) or polyelectrolyte (PVA). Using mixtures of
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21
1
2
3
4 nonionic and anionic surfactants led to essential changes in the morphology of the
5
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7 emulsions. In some cases (e.g. for SLES + Tween 80 mixture), a synergetic effect
8
9
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11 occurs and very low values of the yield stress (approx. 1 Pa) and the apparent viscosity
12
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14 (up to 140 mPa·s) were reached. For emulsions containing up to 50 vol% of water, the
15
16
17
18 minimum value of the apparent viscosity (50-90 mPa·s at 25°C) was reached by using
19
20
21 Triton X-114 with the addition of a polymer stabilizing agent.
22
23
24
25 Decreasing the temperature increased the effect of emulsification. The maximum
26
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28 result at 0ºC (decreasing the viscosity by 3 times in comparison with crude oil at 40°C)
29
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32 was obtained for emulsions stabilized by the mixture of Triton X-114 and HEC. Above
33
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35 25°С, a decrease in the emulsification became weaker. Nevertheless, the minimum
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viscosity of the obtained emulsions was below the necessary level (< 200 mPa·s at high
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42 shear stresses), which is acceptable for tube transportation of oil.
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49 ASSOCIATED CONTENT
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54
The following files are available free of charge.
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22
1
2
3
4 The trademarks, chemical structure, and main physical characteristics of surfactants
5
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7 used in this work are given in Table 1 of Supporting file 1. The designations,
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11 components, and peculiarities of preparing the oil emulsions used in this work are listed
12
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14 in Table 2 of Supporting file 1. The analytical methods used for characterization of all
15
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18 prepared emulsions are also included in this file (PDF_1).
19
20
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22 The photomicrographs and the DSC data for simple water/oil emulsions stabilized by
23
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26 the mixture of Triton X-114 and HEC are presented in Supporting file 2 (PDF_2).
27
28
29
30 The flow curves and the DSC data for water/oil emulsions with 10 vol.% of an aqueous
31
32
33
34 phase are presented in Supporting file 3 (PDF_3).
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36
37
38 AUTHOR INFORMATION
39
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42 Corresponding Author
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46 * e-mail: alex_malkin@mig.phys.msu.ru
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49
50 ACKNOWLEDGMENT
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4 This work was carried out within the State Program of TIPS RAS. The authors are
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7 grateful to Roman S. Borisov (TIPS RAS, Moscow) for GC/MS analysis of heavy crude
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11 oil sample.
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14
15 REFERENCES
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18
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49 Experimental investigation of the effects of various parameters on viscosity reduction of
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heavy crude by oil-water emulsion. Pet. Sci. 2015, 12, 170–176.
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30
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7 transportation. Energy Source. 2002, 24, 93-102.
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21 (43) dos Santos, R. G.; Bannwart, A. C.; Briceño, M. I.; Loh W. Physico-chemical
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32 Des. 2011, 89, 957-967.
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Table 1. The content of main fractions in the maltene part of oil used in this work.
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10
Naftene fractions, wt%
11 Paraffins, Aromatics,
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13 wt% wt%
14 mono- bi- tri- tetra- penta- hexa-
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17 11.09 10.51 27.91 18.82 15.49 3.59 0.00 12.60
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7 Table 2. Values of interface tension for solutions of different surfactants: σL ‒ on the
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11 edge with air, σSL ‒ on the edge with heavy crude oil.
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σL (σSL), mN/m
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18 (at 21±1°С)
19
Surfactant solutions
20 Surfactant
21 Surfactant
22 solution/oi
23 solution/air
24 l
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26 SLES (2.5 wt% in aqueous solution) 33.3 3.9
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29 Tween 80 (2.5 wt% in aqueous solution) 37.6 8.6
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31 1:1 (wt) SLES + Tween 80 (2.5 wt% in aqueous solution) 36.9 6.8
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34 OP-7 (10 wt% in aqueous solution) 32.7 0.6
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36 1:1 (wt) SLES + OP-7 (2.5 wt% and 10 wt% in aqueous
37 32.5 1.5
38 solutions)
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Triton X-114 (2.5 wt% in aqueous solution) 29.7 0.3
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43 1:1 (wt) SLES + Triton X-114 (2.5 wt% in aqueous solution) 31.9 1.8
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HEC + Triton X-114 (0.25 wt% and 5.0 wt% in aqueous
46 27.6 * 0.1 *
47 solution)
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50 Proxanol 228 (2.5 wt% in aqueous solution) 40.6 8.6
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52 Sintanol ALM10 (2.5 wt% in aqueous solution) 32.3 2.3
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55 Rheovis CSP (0.5 wt% in aqueous solution) 73.1 26.5
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33
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4 Sokalan CP10S (10 wt% in aqueous solution) 54.2 10.5
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6 * at 60°С (see, Table 2 in Supporting Information).
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33 Figure 1. GC/MS spectrum of the maltene part of the heavy oil sample.
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38 Image info: TIFF, 24-bit color, 300 dpi, 7×5 inches
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25 Figure 2. The flow curves and temperature dependence of the oil viscosity used in this
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33 Image info: TIFF, 24-bit color, 300 dpi, 3.33×3.01 inches
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23 Figure 3. Typical thermograms for: а) oil/water (w/o/w) emulsion (T4, No.2) and b)
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water/oil emulsion (Eu2, No.1) in cooling (1) and heating (2) modes. The designations
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30 and sample numbers correspond to Table 2 in Supporting Information. Content of the
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aqueous phase in emulsions is 25 vol%.
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Figure 4. Typical photomicrographs of oil/water (a-f) and water/oil (g-l) emulsions (the
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33 designations and sample numbers correspond to Table 2 in Supporting Information).
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36 Content of the aqueous phase in emulsions is 25 vol%.
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21 Figure 5. Comparison of the droplet size of emulsions of the same compositions
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obtained at: a) intensive (sample X2) and b) low-rate emulsification (sample X4),
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28 magnification 4x. c) The flow curves of emulsions (ST4, ST5, T4) obtained at different
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rates of emulsification. Content of the aqueous phase in emulsions is 25 vol%.
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Figure 6. Comparison of compatibility of heavy oil with: a) aqueous solution of surfactant
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31 (SLES + Triton X-114, σSL = 1.8 mN/m) and b) aqueous solution of polyacrylamide
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(Rheovis CSP, σSL = 26.5 mN/m).
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Figure 7. (a) Typical flow curves for oil/water (w/o/w) emulsions at 25°C. (b) Flow curves
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22 for emulsions with anionic surfactant (SLES, S1), nonionic surfactant (Tween 80, T4),
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and their mixture (ST1) at 25°C. (c) The flow curves for emulsions with anionic
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29 surfactant only (SLES, S1), nonionic surfactant OP-7 (OP1) or Triton X-114 (X1) only,
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as well as different binary mixtures of anionic and nonionic surfactants (SOP1 and SX1)
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36 at 25°C. Content of the aqueous phase in emulsions is 25 vol%.
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29 Figure 8. Photomicrographs of emulsions containing aqueous solutions: a) SLES
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33 (sample S1), b) SLES and ОP-7 mixture (sample SOP1), c) ОP-7 (sample OP1), d)
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36 SLES (sample S1), e) SLES and Tween 80 (sample ST1), and f) Tween 80 (sample
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40 T4); for a, b, c – magnification 10x and d, e, f – magnification 40x. Content of the
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43 aqueous phase in emulsions is 25 vol%.
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Figure 9. (a) Flow curves of emulsions with different quantity of surfactant (from 2.5 to
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22 5.0 wt%) and polymer stabilizer (from 0 to 5 wt%) in an aqueous phase at 25°C.
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Content of the aqueous phase: 25 vol% for ST5 (without polymers), 50 vol% for
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29 ST12‒ST14 (with PVA) and for ST15 (with HEC). (b) The flow curves of emulsions with
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50 vol% of the aqueous phase containing different amount of the stabilizing agent HEC:
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36 no polymer (X6), 0.10 wt% (X7), 0.25 wt% (X5), and 0.50 wt% (ST15) at 25°C. (c) Effect
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39 of HEC adding on the stability of emulsions with 50 vol% of the aqueous phase. The
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43 designations of the samples are listed in Table 2 of Supporting Information.
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20 Figure 10. Flow curves of emulsions X5-X10 containing Triton X-114 and 0.25 wt% of
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HEC as a stabilizing agent at different concentration of the aqueous phase (50‒20
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27 vol%): (a) at 0°C; (b) at 25°C; (c) at 40°C.
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1
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4 GRAPHICAL ABSTRACT
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