Petroleum Science and Technology, 27:182196, 2009 Copyright Taylor & Francis Group, LLC ISSN: 1091-6466 print/1532-2459

9 online DOI: 10.1080/10916460701700278

Viscosity of Concentrated Emulsions: Relative Effect of Granulometry and Multiphase Morphology

I. Hnaut,1 A-C. Courbaron,1 and J. F. Argillier1
1 Institut

Franais du Ptrole, Rueil-Malmaison, France

Abstract: High viscosity and high density make heavy and extra heavy crude oils very difcult to produce. They cannot be pumped in their natural state and advanced technologies are required. Formation of oil-in-water emulsions is one of them. A typical emulsion contains 65% of dispersed phase and has a viscosity lower than 500 mPa.s. Current research is aimed at increasing the crude oil content at reduced costs with still good stability and low viscosity. Consequently, an experimental study was dedicated to the relationship between the structure and the rheological properties of heavy oil emulsions. Particular attention was paid to process parameters employed to prepare emulsions. Depending on the shear device, various emulsions have been obtained, either simple or multiple, monodisperse or bimodal. The resulting viscosity is discussed. It is particularly low when the emulsion is either coarse and unimodal or ne and simple. The highest viscosity is obtained when the emulsion is ne and multiple. The experimental results conrm that both composition variables and process parameters have to be taken into account to minimize viscosity of heavy oil emulsions. Keywords: granulometry, heavy crude oil, oil-in-water emulsion, viscosity reduction

INTRODUCTION High viscosity and high density make heavy and extra-heavy crude oils very difcult to produce. They cannot be pumped in their natural state and advanced technologies such as insulation, heat or dilution are required. Despite the substantial operating costs they imply, heavy oils are considered as valuable energy sources. Actually, their reserves are at about the same magnitude as conventional crude oils (Tedeshi, 1991; Saniere et al., 2004). Therefore, further research to promote the development of heavy crude oils is on going. In this way, formation of oil-in-water emulsions to reduce heavy oil viscosity has been largely investigated (Pilhevari et al., 1988; Pal, 1993;
Address correspondence to Isabelle Hnaut, Institut Franais du Ptrole, 1 & 4 avenue de Bois-Prau 92852 Rueil-Malmaison cedex. E-mail: Isabelle.HENAUT@ifp.fr 182

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Zaki, 1997; Romero et al., 2002). The major application of this method is the ORIMULSION (Bitumenes Orinoco S.A., Caracas, Venezuela) process developed in Venezuela to produce energy in thermoelectrical plants (Salager et al., 2001). Two other commercial emulsion pipeline systems for crude transport are known (Zaki et al., 2001), one in Indonesia (Sommer and Simpson, 1983), and one in California (Marsden and Raghavan, 1973). A more recent example is the case of Ku-Maloob-Zaap oileld (Gulf of Mexico) for which a formulation has been developed (Ramirez de Santiago, 2006) to enable the transportation of a 13 API heavy crude oil. The emulsion method consists in dispersing the heavy oil in the form of droplets within water. An emulsifying agent is added in order to lower the interfacial tension between the immiscible liquids and stabilize the emulsion. Formulation parameters are numerous: nature and concentration of surfactants, oil volume fraction, oil viscosity, salinity, etc. These physico-chemical characteristics control the emulsion rheology and especially its viscosity. Process parameters employed to prepare emulsions can also have an important effect. The study presented in this article focuses on this last point. It reports, in particular, how mixing speed changes the viscosity of emulsions having exactly the same formulation.

MATERIALS AND METHOD A rst series of emulsions was prepared with castor oil (from Seatons) and distilled water. In order to stabilize them, an alkylphenol ethoxylated (Triton X405 from Sigma Aldrich, Steinheim, Germany) was dissolved in water with a concentration of 2% weight. All the emulsions contain an oil volume fraction of 70%. They were obtained by gentle stirring of the two liquids (105 ml oil and 45 ml aqueous phase) inside an IKA (Staufen, Germany) agitator tted with a propeller. The mixing lasted 90 sec with a constant speed xed in the range of 5002,000 rpm. An additional emulsion was prepared with the high shear homogenizer Ultra Turrax T25 (IKA, Staufen, Germany) set at 13,000 rpm. The morphology of the samples was characterized by optical microscopy and laser granulometry. differential scanning calorimetry (DSC) was also used to characterize the emulsion type: either simple (oil-inwater) or multiple (water in-oil-in-water) (Clausse et al., 2005). Rheological measurements were performed employing the TA Instruments AR2000 (TA Instruments, Crawley, United Kingdom) controlled stress rheometer with a rough plate and plate geometry and a 2 mm gap. Shear rate sweeps (30 to 300 s 1 ) were carried out within 2 min at 20C. Emulsion preparations and testing were carefully replicated for all the samples. In order to conrm the results, a second series of emulsions was made with a Canadian heavy oil. All the experimental conditions were the same as previously, except that the emulsifying agent had been replaced by one that is less hydrophilic (Triton X114, Sigma Aldrich, Steinheim, Germany).

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Granulometry and Morphology Characterizations Photomicrographs obtained with an optical microscope are shown in Figure 1. They have been taken on castor oil emulsions prepared with various rotational speeds: 835, 1,150, 1,450, 2,000, and 13,000 rpm. The results clearly indicate that a higher mixing speed generates smaller droplets. This correlation between stirring intensity and droplet size was conrmed by laser granulometry. The droplet size distributions determined thanks to this method

Figure 1. Optical microscopy pictures obtained on castor oil-in-water emulsions.

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Figure 2. Droplet size distributions of castor oil-in-water emulsions (laser granulometry).

are presented in Figure 2. They were used to quantitatively characterize the emulsion structure by calculating two statistical diameters: d3;2 (Sauter or volume/surface diameter) and d4;3 (mean volume diameter): X d3;2 D X
i i

ni d 3 ni d
2

X and d4;3 D X
i i

ni d 4 ni d 3 (1)

The ratio d4;3 =d3;2 is evaluated to assess the width of distribution of the emulsions. The lower it is, the more monodisperse the emulsion is. All the data can be found in Table 1. The calculations indicate that the emulsions

Table 1. Statistical diameters of castor oil-in-water emulsions (laser granulometry) Mixing speed (rpm) 1,150 1,450 2,000 13,000

d4;3 ( m) 74 36 12 9

d3;2 ( m) 49 30 9.5 0.9

d4;3 =d3;2 1.5 1.2 1.2 10

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made with a moderate shear are almost unimodal, as it is expected with a high internal phase ratio (HIPR) laminar process (Mason and Bibette, 1996). On the contrary, the emulsion made with the high shear homogenizer appears to be polydisperse with two main diameters centered around 0.1 and 10 m. Granulometry analysis was followed by DSC measurements. As already mentioned, they can indicate whether the emulsion is simple or multiple. Actually, the thermogravimetric curve of a single O/W emulsion appears with a single exothermic crystallization peak corresponding to free water. Unlikely, the thermogravimetric curve of a multiple emulsion displays two exothermic crystallization peaks: one for free water and one at lower temperature for internal phase water. Internal phase water is water that has been nely trapped inside oil droplets and that consequently diminishes the amount of continuous phase in the emulsion. The thermographs of castor oil emulsions are presented in Figure 3. They show that the emulsions prepared at high mixing speed (2,000 rpm with the agitator and 13,000 rpm with the homogenizer) contain only free water. They are simple oil-in-water emulsions. Inversely, the emulsions prepared at moderate shear rates appear as multiple water-inoil-in-water emulsions. It can be noticed that more internal phase water is present as mixing speed applied during preparation decreases. In conclusion, the castor oil emulsions that have been studied can be divided into three classes, namely: monodisperse and multiple emulsions, monodisperse and simple emulsions, and polydisperse and simple emulsions. These emulsions have the same composition and their distinct morphologies only come from the different process parameters applied during their preparation. The same set of structural characterizations was performed on heavy crude oil emulsions. Due to the opacity of the samples, optical microscopy was carried out on dilute emulsions. The pictures are shown in Figure 4. Laser granulometry and DSC measurements are respectively presented in Figures 5 and 6. These experimental results conrm that increasing the mixing speed of preparation leads to different emulsions: going from unimodal and multiple water-in-oil-in-water emulsions to polydisperse and simple oil-inwater emulsions. In the case of the multiple heavy oil emulsions, the presence of internal phase water can be explained by the action of the asphaltenes. Actually, these petroleum molecules are known to be surface active and to stabilize water-in-oil emulsions (Mc Lean and Kilpatrick, 1997; Jeribi et al., 2002). It is well known that the structural characteristics of emulsions inuence their viscosity. The aim of the study is to select which one of the three identied emulsion classes minimizes viscosity.

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Figure 3. Thermographs of castor oil emulsions prepared with different mixing speeds. (continued)

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Figure 3. (Continued)

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Figure 4. Optical microscopy pictures obtained on heavy crude oil-in-water emulsions.

Rheological Characterization Rheological characterization was performed on both series of emulsions. It focuses on continuous measurements as viscosity is the main criterion to classify the emulsions. A viscoelastic study comprising oscillatory tests was also undertaken but it is out of the scope of the present article. Flow curves are presented in Figure 7 for castor oil emulsions and in Figure 8 for heavy crude oil ones. In each case, the response of the pure oil has also been included and shows that its viscosity is much higher than the one of emulsions. This result conrms that oil-in-water emulsication is an efcient method to improve heavy crude oil transportation. In order to emphasize the inuence of process parameters on ow properties of emulsion, viscosity was

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Figure 5. Droplet size distributions of heavy crude oil-in-water emulsions (laser granulometry).

plotted as a function of mixing speed. The graphs obtained for both types of emulsions (Figures 9 and 10) are quite similar: they show an increase in viscosity which is followed by a decrease. This complex evolution has been interpreted in terms of structural differences. It is explained in the next section.

DISCUSSION Both structural and rheological experiments conrm that emulsions having the same composition can have various morphologies and ow properties as soon as they are prepared in different conditions. The aim of the study was to relate these interacting parameters in order to select conditions that minimize emulsion viscosity. The relation between mean droplet diameter and viscosity had already been observed (Otsubo and Prudhomme, 1994) for concentrated oil-in-water emulsions. It was found that viscosity increases with decreasing droplet size. This situation results from the higher total interfacial area with the diminishing of droplet diameter. For concentrated emulsions, drops come to contact, they get deformed, and then compressed. In this case, the liquid lms separating adjacent droplets strongly affect the emulsion viscosity. This phenomenon generates the rst increase in viscosity observed in Figures 9 and 10. Actually, the increase of the mixing speed from 200 to 1,000 rpm results in a strong decrease in droplet size, which in turn rises the viscosity. The most striking result is that emulsions prepared at higher mixing speed are less

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Figure 6. Thermographs of heavy crude oil emulsions prepared with different mixing speeds. (continued)

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Figure 6. (Continued)

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Figure 7. Flow curves of castor oil emulsions prepared with different mixing speeds (T D 20 C).

viscous despite their smaller droplet diameter. Two reasons can be suggested. Concerning the emulsions prepared at 2,000 rpm, it can be noticed that they are not multiple anymore. Actually, the high shear induces the rupturing of multiple droplets and internal phase water is liberated in the aqueous continuous phase (Florence and Whitehill, 1982). As emulsions contain more free water, their dispersed phase volume fraction appears lower and causes

Figure 8. Flow curves of heavy crude oil emulsions prepared with different mixing speeds (T D 20 C).

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Figure 9. Viscosity (at 36 s speeds (T D 20C).

1)

of castor oil emulsions prepared with different mixing

a viscosity decrease. The second reason is that emulsions prepared with a very high shear rate seem to be bimodal. It is known that for a xed volume of dispersed phase, the viscosity of a concentrated bimodal size distribution emulsion is lower than the one with a unimodal size distribution (Chang and Powell, 1994). The decrease is explained by the empty spaces existing between coarse droplets being lled with ne droplets.

Figure 10. Viscosity (at 36 s mixing speeds (T D 20 C).

1)

of heavy crude oil emulsions prepared with different

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CONCLUSIONS Physicochemical formulation is known to inuence rheological properties of emulsions. Nevertheless, we have shown that mixing speed is also a predominant parameter. Depending on the stirring intensity, the emulsion is either unimodal and multiple, unimodal and simple, or polydisperse and simple. Using a low shear device is advantageous because it costs less energy. It leads to unimodal low viscous emulsions with coarse droplet diameter. The produced emulsions can also be multiple, which increases viscosity. This rise can be counteracted by a higher surfactant concentration. Although it costs more energy, using a high shear device can lead to low viscous bimodal and single emulsions. An in-between zone producing ne and multiple emulsions is to be avoided. This study shows that both composition variables and process parameter have to be taken into account to minimize viscosity of heavy crude oil emulsions.

ACKNOWLEDGMENTS The authors gratefully acknowledge C. Dalmazzone (IFP) for helpful discussions about DSC measurements.

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