Journal of Petroleum Science and Engineering 69 (2009) 189192

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Journal of Petroleum Science and Engineering

Research paper

The synergetic effect between heavy oil components and emulsier in heavy oil-in-water emulsion
Jinmei Bai a,, Tongyao Zhang b, Weiyu Fan c
a b c

E-tech Oileld Technology Development Co., Ltd. Tianjin, 300384, China Institute of Oil Recovery Engineering CNOOC, Tanggu, Tianjin, 300452, China State Key Laboratory of Heavy Oil Processing in China University of Petroleum, Shandong, 257061, China

a r t i c l e

i n f o

a b s t r a c t
Resin and asphaltene were extracted from Gudao and Liaohe heavy oil by using the adsorption chromatography. Toluene and n-dodecane were selected as model oil, sodium dodecylbenzene sulfonate was selected as emulsier. The interfacial tension (IFT) was investigated without emulsier and adding emulsier, the effect of pH value on the interfacial tension was also investigated. The results show that the interaction between component and emulsier lies on the interfacial activity of components, and the higher interfacial activity is, the stronger interaction is. And the inuence of pH on IFT is great at acid and base conditions, but little at neutral condition. The synergetic effect between polar component and emulsier is stronger in the neutral condition and weak acid and base conditions. Crown Copyright 2009 Published by Elsevier B.V. All rights reserved.

Article history: Received 24 December 2007 Accepted 10 August 2009 Keywords: heavy oil components emulsiers interaction pH value interfacial tension

1. Introduction Emulsicationviscosityreduction is an important area of exploitation, pipeline transportation and processing of heavy oil. Researchers have studied the preparation and application of heavy oil-in-water emulsion (Zaki, 1997; Ahmed and Amal, 1999), but they did little research about the mechanism of emulsication and stabilization of heavy oil-in-water emulsion (Fan et al., 2001). They were only interested in the stability of heavy oil emulsion (McLean and Kilpatrick, 1997; Yang and Lu, 1998; Li, 1998). In order to widely apply emulsicationviscosityreduction technology, research about the mechanism of emulsication and stabilization of heavy oil-inwater emulsion should be studied in-depth. The bad adaptability of emulsiers and the unmanageable stabilization were caused by the differences of heavy oil components. The interaction between heavy oil components and emulsiers is the core of heavy oil-in-water emulsion's formation and stabilization. In this paper, resin and asphaltene was extracted from Gudao and Liaohe heavy oil with the method of adsorption chromatography. Toluene and n-dodecane were selected as model oil, sodium dodecylbenzene sulfonate(LAS) was selected as emulsier. The interfacial tension was investigated. When emulsier was added and before it was added, the effect of pH value on the interfacial tension was investigated separately.

2. Experimental Table 1 gives basic properties of Liaohe Du-84 heavy oil and Shengli Gudao heavy oil. Isolate heavy oil to polar components: the method to obtain polar components (saturate, aromatic, resin and asphaltene) is based on the Chinese petroleum industry standard method (SH/T 0509-92).The main conditions are as follows: Isolation of asphaltene: heavy oil:n-heptane = 1 g:50 mL; isolation of soluble fractions: 75150 m neutral Al2O3 columns. Acid number: using 0.1 M KOH/ethanol as titrant, V(toluene):V (hexamethylene):V(anhydrous ethanol):V(water) = 100:50:49:1 as titration solvent, pHS-3C pH value meter. Base nitrogen number: using perchloric acid/caproic acid as titrant, V(toluene):V(caproic acid) = 10:20 as titration solvent, then determining variation of electric potential (mV) with the volume of titrant (V), the point whose derivatives are the largest on the graph of mV versus V is the terminal point of titration. Ultimate analysis: Elementar Analy Sensysteme GmbH Vario Elc III ultimate analysis instrument (German). Determination of interfacial tension: interfacial tension of oil water is measured by spinning drop method at 50 C, using XZD-3 interfacial tension apparatus. Preparation of oil/water system: heavy oil, resin and asphaltene were regarded as solute; toluene and n-dodecane (W(toluene):W (n-dodecane) = 1:1) were selected as mix solvent, a series of model

Corresponding author. E-mail address: baijinmei_1982@hotmail.com (J. Bai).

0920-4105/$ see front matter. Crown Copyright 2009 Published by Elsevier B.V. All rights reserved. doi:10.1016/j.petrol.2009.08.008

190 Table 1 Basic properties of Liaohe and Gudao heavy oil. Heavy oil Gudao LiaoheDu-84 Density (20 C)/ (g cm 3) 0.9934 1.0001

J. Bai et al. / Journal of Petroleum Science and Engineering 69 (2009) 189192

Viscosity (80 C) /(mm2 s 1) 810.38 4898.92

Solidication point/ C 8.5 42

Acid number/ mg KOH g 1 3.25 9.05

Gudao is a production base of heavy oil in Shengli Oil eld which is the second oil eld of China. Liaohe Oil eld is the third oil eld of China, most of its reserve is heavy oil.

oil containing 0.55% (w/w) solute were prepared. Sodium dodecylbenzene sulfonate was selected as emulsier. According to the experimental demand, the variational aqueous phase was deionized water, de-ionized water in different pH value, or emulsier aqueous solution. 3. Results and discussion 3.1. Elemental properties of two kinds of heavy oil and their polar components The elemental properties of two kinds of heavy oil and their polar components as shown in Table 2 can reveal the following results: The sequence of fractions content is: resin > aromatic > saturate > asphaltene. Compared with Gudao heavy oil, there are more resins and less asphaltenes in Liaohe heavy oil. The acid number of two kinds of heavy oil and their fractions suggests that they are different in the distribution of acid number and the composition of acidic substance. The nitrogen number of two kinds of heavy oil and their fractions indicates that they are different in the composition of basic nitride. The results of ultimate analysis got the conclusion that: compared with Gudao heavy oil and its corresponding components, the Liaohe heavy oil and its polar components have higher degree of unsaturation, higher content of nitrogen and oxygen, and higher acid number. And most of nitrogen and oxygen atoms consist in resin and asphaltene. Basic properties showed that there are more differences between two kinds of heavy oil and their polar components, which make it easy to review the inuence of component difference on interfacial property in the study. 3.2. Comparison of interfacial activities of two kinds of heavy oil and their polar components Interfacial tension is the most important parameter of oilwater interfacial property. It affects the adsorption rata and adsorbed
Table 2 Elemental properties of two kinds of heavy oil and their polar components. Heavy oil fractions Distribution/% Acid number/mg KOH g 1 3.25 9.05 0.23 0.22 2.79 9.74 Nitrogen number/g g 1 13441 8106 13671 13149 13212 20830

amount of polar components in oil/water interface and also affects the interfacial structure. It is the appearance of interaction between polar components and emulsier. In order to compare two kinds of heavy oil and their polar components' interfacial activity, the inuence of dosage of heavy oil and its polar components in simulated oil on oilwater interfacial tension was studied. Table 3 shows the results. Blank interfacial tension is the oil/water interfacial tension of blank model oil and de-ionized water without components. The data of Table 3 show that the existence of heavy oil and polar components reduce the oil/water interfacial tension of model oil, and the tendency of oil/water interfacial tension reduces with the increasing of polar components' contents. Results indicate that the adsorbed amount of natural surfactant existing in crude oil increases with the increasing of polar components' contents, it goes into saturation under certain concentrations. Interfacial pressure is the variation of the oil/water interfacial tension with and without surfactant. = is the symbol for interfacial pressure, stands for the oil/water interfacial tension without surfactant, stands for the oil/water interfacial tension with surfactant. Interfacial pressure is the symbol of interfacial activity. Interfacial pressure increases with the adsorbate amount of surfactant in surface. The larger interfacial pressure in the same concentration, the stronger the ability of reducing interfacial tension will be. Table 4 gives the inuences of heavy oil and its components amount in model oil on oilwater interfacial pressure. The data of Table 4 show that the interfacial pressure of two kinds of heavy oil and their polar components are different in the same concentration, that is, their interfacial activities are different. The sequence of the interfacial activity (IFA) of Gudao heavy oil and its polar components is IFA (heavy oil) > IFA(resin) > IFA (asphaltene). The sequence of the IFA of Liaohe heavy oil and its polar components is IFA (asphaltene) > IFA(heavy oil) > IFA (resin). The interfacial activity of Liaohe heavy oil and its polar fractions is superior to that of Gudao. From elemental properties and the IR spectrum of asphaltene, we can know there are hydroxide radical, amidocyanogen, carbonyl group and carboxyl in asphaltene molecule, and Liaohe asphaltene has more than others, so there is more hydrogen bond in asphaltene which leads to stronger interfacial activity of asphaltene (Fig. 1). 3.3. Effects of the interaction of heavy oil components and emulsiers on interfacial tension In order to review the inuences of the interaction between components and emulsier on interfacial tension, the variation of interfacial tension with the concentration of fractions in the model oil with 1% emulsier was studied. Table 5 gives the results.

Element fractions/% C 84.01 86.50 86.73 87.07 84.25 87.87 82.97 85.53 80.62 81.92 H 10.92 10.91 13.12 12.87 10.70 10.57 9.85 9.93 8.72 8.65 N 0.57 0.81 0 0 0.24 0.34 1.39 1.74 1.21 1.71 O 0.64 1.33 0 0 0.19 0.19 1.40 1.57 1.96 3.13 S 3.31 0.42 0 0 4.16 4.16 3.99 0.55 6.37 0.51

n(H)/n(C)

Gudao heavy oil Liaohe heavy oil Gudao saturates Liaohe saturates Gudao aromatics Liaohe aromatics Gudao resins Liaohe resins Gudao asphaltenes Liaohe asphaltenes

25.08 26.07 31.39 28.49 34.88 41.65 6.65 3.38

1.56 1.51 1.82 1.77 1.52 1.44 1.42 1.39 1.30 1.26

The amount of resins is calculated according to difference; the amount of oxygen is the actual value examined.

J. Bai et al. / Journal of Petroleum Science and Engineering 69 (2009) 189192 Table 3 The inuences of heavy oil and its components amount in model oil on oilwater interfacial tension. Model oil /mNm 1 Blank Gudao heavy oil Gudao resins Gudao asphaltenes Liaohe heavy oil Liaohe resins Liaohe asphaltenes 41.45 41.45 41.45 41.45 41.45 41.45 0.5% 26.84 34.96 35.30 22.82 39.54 9.96 1.0% 25.44 34.58 34.91 21.74 32.22 8.15 2.0% 24.44 31. 90 32.85 17.84 31.91 8.13 3.0% 24.06 27.35 31.02 17.08 25.37 8.01 4.0% 23.63 26.89 29.55 16.17 23.79 7.94 5.0% 23.02 25.14 27.57 14.95 23.65 7.32 Gudao heavy oil Gudao resins Gudao asphaltenes Liaohe heavy oil Liaohe resins Liaohe asphaltenes

191

Table 5 The variation of interfacial tension with the concentration of fractions in the model oil (with 1% emulsier). Model oil /mNm 1 Blank 3.28 3.28 3.28 3.28 3.28 3.28 0.5% 2.85 3.33 3.41 2.79 3.08 1.30 1.0% 2.55 2.93 3.22 2.62 3.31 0.70 2.0% 2.34 2.74 3.34 1.95 3.16 0.25 3.0% 2.44 2.82 3.06 1.94 3.67 0.29 4.0% 2.43 2.95 3.16 1.93 3.26 0.35 5.0% 2.40 2.89 3.02 1.95 3.62 0.35

Table 4 The inuences of heavy oil and its components amount in model oil on oilwater interfacial pressure. Model oil /mNm 1 Blank Gudao heavy oil Gudao resins Gudao asphaltenes Liaohe heavy oil Liaohe resins Liaohe asphaltenes 0 0 0 0 0 0 0.5% 14.61 6.49 6.15 18.63 1.91 31.49 1.0% 16.01 6.87 6.54 19.71 9.23 33.30 2.0% 17.01 9.55 8.60 23.61 9.54 33.32 3.0% 17.39 14.10 10.43 24.37 16.08 33.44 4.0% 17.82 14.56 11.90 25.28 17.66 33.51 5.0% 18.43 16.31 13.88 26.50 17.80 34.13

Table 6 The variation of interfacial tension difference with the concentration of fractions in the model oil (with 1% LAS). Model oil /mNm 1 Blank Gudao heavy oil Gudao resin Gudao asphaltene Liaohe heavy oil Liaohe resin Liaohe asphaltene 0 0 0 0 0 0 0.5% 0.43 0.05 0.13 0.49 0.20 1.98 1.0% 0.73 0.35 0.06 0.66 0.04 2.58 2.0% 0.94 0.54 0.06 1.33 0.12 3.03 3.0% 0.84 0.46 0.22 1.34 0.40 2.99 4.0% 0.85 0.33 0.12 1.35 0.02 2.93 5.0% 0.88 0.39 0.26 1.33 0.34 2.93

Blank interfacial tension is the interfacial tension of blank model oil and 0.1% LAS water solution without components. In order to compare the effect of the interaction between fractions and emulsier on interfacial tension, the difference of after and before adding components in xed concentration of emulsier as a parameter was made which is similar to interfacial pressure, and marked as . Table 6 gives the variation of under different concentrations of fractions. The results of Table 5 as follows: after the addition of heavy oil and polar component, the interfacial tension is lower than the blank. The fact indicates the interaction between natural surfactants in heavy oil and emulsier reduces the interfacial tension. The data of Table 6 reveal that the interaction between different fractions and emulsier did different effects on interfacial tension. The large interfacial activity fraction Liaohe asphaltene shows stronger cooperation. But the Gudao asphaltene and Liaohe resin of weak interfacial activity did little on the interfacial tension, this fact indicates that there wasn't distinct co-operation between them and emulsier. All in all, the interaction between heavy oil component and emulsier depends on the interfacial activity of heavy oil and its

components, the more active of component, the higher interaction it is. 3.4. Effect of pH value on interfacial tension of simulated oil system Aqueous phase is one of the dominant factors of emulsion's interfacial property. The effects of pH value on interaction between fractions and emulsier have been studied. The data of Figs. 25 indicate the effects of pH value of aqueous on interfacial tension. We can obtain regularity from Figs. 2 and 3 that before being added emulsier, the IFT of the two kinds of heavy oil and its polar components simulated oil and de-ionized water vary as follows. When it is pH < 7, the interfacial tension increases with the increasing of pH value. When it is pH > 7, the interfacial tension begins to reduce; the interfacial tension at the basic condition is lower than that in the acidic condition. The results above show that the interfacial activity of heavy oil and its polar fraction is great at basic conditions. The interfacial tension of model oil system changed with pH value after being added 1% emulsier. The results are shown in Figs. 4 and 5. We can know from Figs. 3 and 4 that after being added 1% emulsier, the interfacial tension of the blank model oil is lower in the

Fig. 1. IR spectrum of Gudao and Liaohe asphaltene.

Fig. 2. The inuences of pH value on IFT of Gudao heavy oil and its polar components model oil/de-ionized water. (1) 5% Gudao asphaltenes model oil, (2) 5% Gudao heavy crude model oil and (3) 5% Gudao resins model oil.

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Fig. 3. The inuences of pH value on interfacial tension of Liaohe heavy oil and its polar components model oil-de-ionized water. (1) 5% Liaohe resins model oil, (2) 5% Liaohe heavy crude model oil and (3) 5% Liaohe asphaltenes model oil.

Fig. 5. The inuences of pH value on interfacial tension of Liaohe heavy oil and its polar components model oil and 1% emulsier in water. (1) 5% Liaohe resins model oil, (2) blank model oil, (3) 5% Liaohe heavy crude model oil and (4) 5% Liaohe asphaltenes model oil.

strong acidic and strong basic conditions, and it is even lower in the strong acidic condition, but the adding of heavy oil and their polar components doesn't change their interfacial tension much. That is, there is no distinct interaction between emulsier and components in the strong acidic and basic conditions. In the neutral and weak acidic and basic conditions with a pH value from 4 to 10, the adding of heavy oil and its polar components lowers the interfacial tension obviously and shows distinct interaction. This fact indicates that the inuence of pH is great at neutral, weak acidic and basic conditions, but little at strong acidic and basic conditions. The interfacial activity of emulsier is stronger than that of heavy oil and its polar fractions, the strong acidic and basic conditions cover up components' interfacial activity, but the stronger Liaohe heavy oil and its asphaltene show interaction in some way. Comparatively, the emulsier's adsorptive capacity in interface reduces in the neutral and weak acidic and basic conditions, and the heavy oil and its polar components adsorb competitively in interface, co-operate with emulsier, and they reduce the interfacial tension together. This fact attests that there is large interaction between heavy oil and its polar fraction and emulsier in the neutral and weak acidic and basic condition.

degree of unsaturation, higher content of nitrogen and oxygen, higher acid number and relatively stronger interfacial activity. (2) Liaohe asphaltene, which has a stronger interfacial activity, can reduce the oilwater IFT, shows a stronger synergetic effect with emulsier; Gudao asphaltene and Liaohe resin, which have a weaker interfacial activity, do not show any clear synergetic effect with emulsier. The interaction between polar component of heavy oil and emulsier lies on the interfacial activity of polar component: the stronger interfacial activity of component, the stronger interaction it is. (3) In the strong acidic and basic conditions, there is no distinct synergetic effect between emulsier and components; In the neutral and weak acidic and basic conditions with a pH value from 4 to 10, the IFT reduces obviously with the adding of heavy oil and its polar components, and shows stronger synergetic effect. This fact approves that there is interaction between heavy oil and its polar components and emulsier. References
Ahmed, Nehal S., Amal, M.F., 1999. Formation of uid heavy oil-in-water emulsions for pipeline transportation. Fuel 78 (3), 593600. Fan, Wei-yu, Chen, Shu-kun, Yang, Meng-long, et al., 2001. Study on stability of heavy crude oil in water emulsion III oil/water surface tension for heavy crude components and water system. Acta Petrol. Sin. (Petrol. Process. Sect.) 17 (5), 16. Li, M.Y., 1998. Investigation of stability of water-in-crude oil emulsion VI properties of interfacial lm and stability of crude oil emulsion. Acta Petrol. Sin. (Petrol. Process. Sect.) 14 (3), 14. McLean, J.D., Kilpatrick, P.K., 1997. Effects of asphaltene solvency on stability of water in crude oil emulsions. J. Colloid Interface Sci. 189, 242253. Yang, Xiao-li, Lu, Wan-zhen, 1998. Advances in stabilization and destabilization of water in crude oil emulsion. Oileld Chem. 15 (1), 8796. Zaki, Nael N., 1997. Surfactant stabilized crude oil-in-water emulsion for pipeline transportation of viscous crude oil. Colloids Surf. 125 (1), 1925.

4. Conclusion (1) Compared with Gudao heavy oil and its corresponding components, the Liaohe heavy oil and its polar components have higher

Fig. 4. The inuences of pH value on IFT of Gudao heavy oil and its polar components model oil and 1% emulsier in water. (1) blank model oil, (2) 5% Gudao asphaltenes model oil, (3) 5% Gudao heavy model oil and (4)5% Gudao resins model oil.