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Journal of Petroleum Science and Engineering 32 (2001) 145 149 www.elsevier.

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Microemulsion systems applied to breakdown petroleum emulsions


Tereza Neuma de Castro Dantas *, Afonso Avelino Dantas Neto, Everlane Ferreira Moura
Deptos de Qumica e Eng. Qumica, Universidade Federal do Rio Grande do Norte, Campus Universitario s/n, 59072.970, Natal/RN, Brazil

Abstract Microemulsion systems obtained using commercial surfactants with demulsifier and emulsion prevention properties have been employed to break down Brazilian crude water-in-oil (W/O) emulsions. These crude oils were supplied by the Brazilian oil companyPETROBRASand were characterized by the different Balance sheet of Sediment and Water (BSW) values of 48%, 36%, and 32%. The microemulsion systems formed in this study were composed of an aqueous phase (HCl 5.2% solution); an oil phase (toluene); a cosurfactant/surfactant (C/S) phase (isopropyl alcohol (C)/surfactants (S) with a ratio C/S of 9.0). The microemulsion efficiency to break down oil emulsions was evaluated by a direct contact method between the microemulsions and crude (W/O) emulsions. The Scheffe net statistical planning for mixtures was used to relate the component mass fractions to the relative breakdown of petroleum emulsions. The best composition of the microemulsion system for the complete breakdown of oil emulsions with high BSW values had the lowest C/S phase percentage. D 2001 Elsevier Science B.V. All rights reserved.
Keywords: Microemulsion; Petroleum; Emulsion breakdown and surfactants

1. Introduction Fluids injected during the drilling process, with the aim of cleaning up the well, can cause formation damages due to rock pore clogging. Acid solutions, added later to restore the permeability of the rock, can promote the formation of highly viscous emulsions and dregs that will cause a significant reduction of production and even compromise viable economic exploitation. The formation of emulsions and dregs
Corresponding author. Fax: +55-84-2153770. E-mail address: tereza@linus.quimica.ufrn.br (T. Neuma de Castro Dantas).
*

is a serious problem during well stimulation processes and can result in large loss of oil. According to Castro Dantas and Sousa (1995), these losses can amount to around 55%. Many studies have been proposed to break down emulsions. Kosaric et al. (1987) used microbial biomass to break down synthetic emulsions of kerosene/ water, Fang et al. (1988) used microwaves, while Salager (1990) studied the in situ formation of microemulsion systems that can chemically dehydrate the emulsions. Krawczyk et al. (1991) determined important parameters for the evaluation of the performance of demulsifier agents, and Zaki et al. (1996) and Abdel-Azim et al. (1998) studied the efficiency of

0920-4105/01/$ - see front matter D 2001 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 0 - 4 1 0 5 ( 0 1 ) 0 0 1 5 6 - 5

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polyoxyethylenated Bisphenol-A and polyoxyalkylenated amines in the breakdown of synthetic water/ benzene emulsions stabilized by asphaltenes to simulate natural water/petroleum emulsions. In Brazil, PETROBRAS has long been trying to solve the emulsion problems, by promoting unfavourable conditions for emulsion and dregs formation through the use of commercial surfactants with demulsifier and emulsion prevention properties. The absence of basic and fundamental formulations of emulsion breakdown systems for general use in different well conditions provided the motivation for this research. In this work, the performance of microemulsion systems as an alternative in the breakdown of petroleum emulsions and enhancement of oil recovery is investigated.

2. Material and methods The oil samples that were studied were obtained from the following wells: sample 1AP-31/Natal-BR (BSW = 49%); sample 2PXA-07/Xare u-BR (BSW = 38.4%) and sample 3SPM-20/PAT-3/ Natal-BR (BSW = 36%); where BSW is the Balance sheet of Sediment and Water. Ten microemulsion systems were designed with the following composition: aqueous phase5.2% HCl; oil phasetoluene; a C/S phaseisopropyl alcohol/surfactant for each system, with a (C/S) ratio equal to 9.0. The commercial surfactants used were Dissolvan (CLARIANT), NE-8 (BJ SERVICES), Dentrol (CONAB), OC595 (POLAND QUIMICA),

Fig. 1. Ternary diagrams representing the microemulsified systems for surfactants NE-8 (a) and Dissolvan (b) with large and small microemulsion areas, respectively.

Fenoil (BAY ER DO BRASIL), Polimus-43 (POLAND QUIMICA), NE-9 (BJ SERVICES), Poli mus-22 (POLAND QUIMICA), Dehydet (POLAND QUIMICA) and Ultrapan (PETROBRAS).

Table 1 Experimental matrix with microemulsion points Mass fractions XC/S A B C D E F G H I J 0.60 0.60 0.60 0.75 0.75 0.90 0.70 0.65 0.65 0.80 XACID 0.35 0.20 0.35 0.20 0.05 0.05 0.15 0.25 0.25 0.10 XOIL 0.05 0.20 0.05 0.05 0.20 0.05 0.15 0.10 0.10 0.10

Fig. 2. Schematic representation of experimental points within the microemulsion region (Scheffe net).

T. Neuma de Castro Dantas et al. / Journal of Petroleum Science and Engineering 32 (2001) 145149 Table 2 Breakdown efficiency (%P) of petroleum emulsionsample 1 Petroleum sample 1AP-31 Dissolvan A B C D E F G H I J 98.29 97.28 100.00 94.32 89.34 82.65 84.59 55.10 49.79 46.85 NE-8 59.38 97.28 88.33 94.32 50.43 90.43 92.37 38.77 33.47 30.53 Dentrol 82.72 85.60 88.33 86.54 85.45 86.54 84.59 79.59 82.45 79.51 OC595 59.38 54.47 64.98 51.59 85.45 74.86 37.90 20.41 20.32 32.65 Fenoil 82.72 54.47 41.63 82.65 85.45 90.43 61.25 63.26 82.45 87.67 Polimus43 90.51 85.60 72.76 82.65 93.23 43.74 50.66 87.75 82.45 87.67 NE-9 94.40 97.28 96.11 90.50 93.23 90.43 84.59 51.02 49.79 55.02 Polimus22 90.50 86.38 99.92 82.65 85.45 90.43 84.59 79.59 74.29 71.35 Dehydet 51.59 3.89 36.18 28.17 23.19 59.30 6.77 6.12 41.63 14.2

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Ultrapan 80.57 85.71 88.65 80.57 69.38 88.73 62.28 79.59 74.28 46.85

Table 3 Breakdown efficiency (%P) of petroleum emulsionsample 2 Petroleum sample 2Xareu Dissolvan A B C D E F G H I J 58.65 5.20 15.62 48.23 62.29 68.96 40.31 18.21 2.60 10.42 NE-8 48.23 52.08 66.14 68.96 83.13 79.38 92.29 80.73 100.00 80.63 Dentrol 1.56 1.56 66.15 6.25 6.25 1.56 40.21 80.73 84.38 85.83 OC595 58.65 53.12 66.15 58.54 51.87 58.54 50.2 28.64 42.71 44.27 Fenoil 37.81 31.14 55.73 69.06 72.29 68.96 71.46 49.48 47.92 91.04 Polimus43 48.23 41.66 86.98 68.96 82.81 79.27 100.00 59.89 63.02 59.79 NE-9 48.23 41.04 55.73 34.89 72.71 68.37 81.86 59.89 47.92 70.21 Polimus22 79.58 62.50 66.04 68.96 67.19 79.37 61.04 65.10 42.71 49.37 Dehydet 48.23 41.66 66.15 58.54 51.87 68.96 50.73 28.65 37.50 49.37 Ultrapan 81.98 78.12 76.66 81.98 83.33 87.19 84.69 28.64 50.10 38.96

The determination of the microemulsion range systems was carried out by titration of different components of the system until the observation of a transparent solution.
Table 4 Breakdown efficiency (%P) of petroleum emulsionsample 3 Sample 3SPM-20 Dissolvan A B C D E F G H I J 48.96 68.00 74.46 84.96 87.84 84.96 86.88 75.00 67.77 86.00 NE-8 97.04 100.00 90.40 92.96 99.84 92.96 90.88 97.22 100.00 97.11 Dentrol 61.04 72.00 74.40 84.96 79.80 76.9 78.8 75.00 78.88 16.66 OC595 52.96 44.00 50.80 44.96 55.84 52.96 46.96 30.55 67.77 52.66 Fenoil 61.04 64.00 50.40 68.96 71.84 68.96 62.90 52.77 73.33 97.11

The microemulsion efficiency to break down oil emulsions was evaluated by direct contact method between the microemulsions and crude (W/O) emulsions in graduated centrifuge tubes for 30 min under

Polimus43 100.00 96.00 98.72 84.96 87.84 84.96 86.96 100.00 100.00 100.00

NE-9 97.04 72.00 74.80 68.96 87.84 84.96 78.88 86.11 95.55 86.00

Polimus22 76.88 87.92 82.80 68.96 71.84 76.96 86.72 86.11 90.00 86.00

Dehydet 45.04 44.00 58.50 44.96 71.84 60.96 46.96 41.66 56.66 52.66

Ultrapan 92.39 77.77 87.33 93.00 94.44 98.55 95.88 75.00 78.88 74.88

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Table 5 Equations for models representing microemulsified systems in the breakdown efficiency of petroleum emulsions Petroleum Sample 1 Sample 2 Sample 3 Surfactants Dissolvan NE-8 Polimus 43 NE-8 Isoresponse models %P = 305.760XC/S + 14334.649XO 19578.222.XC/S.XO + 2223.849XA 3386.222XC/S.XA 58513.556XOXA + 70766.667XC/S.XO.XA %P = 14.080XC/S 6286.269XO + 8636.667XC/SXO 430.069XA + 702.444XC/SXA + 15145.556XOXA %P = 96.261XC/S + 343.238XO 391.572XC/SXO + 439.917XA 3391.643XOXA + 5421.176XC/SXOXA %P = 45.540XC/S 2379.299XO + 3554.333XC/SXO 479.499XA + 960.111XC/SXA + 14291.556XOXA

stirring at 70 C (Castro Dantas and Sousa, 1995). The emulsion breakdown percentages were calculated using Eq. (1). %P V V0 100 V0 1

where V0 is the oil volume and V is the water volume obtained after breakdown. The experimental plan followed the Scheffe net type II (Goupy, 1988; Ramos et al., 1997), which was applied to the mixtures. In the particular case of the three constituents, emulsion breakdown varies according to the relative concentration at each point of a restricted region of the equilateral triangle inside the micro-

emulsion system domain. The experimental matrix with a previously defined composition in mass fraction is presented in Table 1. Using the compositions and experimental responses, a statistical model, whose coefficients were calculated by multiple regression analysis, according to the least square method (Forestier et al., 1985; Cornell, 1990), was obtained to provide more information on the overall behavior of the system. 3. Results and discussion The microemulsion system can be represented by pseudo ternary diagrams (Fig. 1) where the micro-

Fig. 3. Diagrams representing the domain areas of the Scheffe net for the breakdown efficiency (%P) in (a) sample 1 (Dissolvan), (b) sample 2 (NE-8), (c) sample 3 (Polimus 43), and (d) sample 3 (NE-8).

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emulsion areas are depicted. All the microemulsion systems used in this study showed this same behavior. Fig. 2 represents the Scheffe net used for the oil emulsion breakdown in all microemulsion systems investigated in this work. The points A to J represent different compositions in the mass fraction of microemulsion phases used to break down the oil emulsion. The results showed good percentage breakdown emulsions for all systems. Data obtained from all oil samples are shown in Tables 2 4. The best results were obtained for NE-8 and Polimus-43, where complete breakdown of emulsions of samples 2 and 3 were obtained. The same result was obtained with Dissolvan for sample 1. These results indicate that the breakdown efficiency is directly dependent on the microemulsion composition and the physicochemical oil properties. The results showed in Tables 2 4 allow us to apply a data statistical treatment to give a predictive model that represents the behavior for each system in the studied microemulsion regions. That is, other points (within the experimental domain) can theoretically be obtained from these models. According to the microemulsion breakage profile, a statistical analysis predicted the best range of emulsion breakdown through the isoresponse diagrams, using a confidence value at the 95% level. For each model, specific isoresponse diagrams were generated and analyzed, and the models for the most efficient systems are presented in Table 5. In Fig. 3, the regions of maximum efficiency inside each microemulsion system diagram can be visualized. Fig. 3a shows that the Dissolvan can efficiently be used in microemulsion systems whose composition are in the oil-rich phase and with C/T percentages from 60% to 82%, to break down 100% of the oil emulsion of sample 1. The NE-8 showed to be efficient in aqueousrich phase microemulsion regions for all C/T percentages, completely breaking down the oil emulsion of samples 2 and 3. For sample 3, another system showed to be efficient. This system can use the Polimus-43 in oil-rich and/or aqueous-rich phase microemulsion regions to obtain 100% of emulsion breakdown.

pletely break down oil emulsions formed during production operations of Brazilian petroleum fluids. However, for the most efficient microemulsion system, it is required to test every sample, as the water content in the oil samples (BSW) has a strong effect on emulsion breakdown. These results suggest the possibility of using microemulsion systems in a more efficient and economic way for crude oil recovery and other applications in oil fields.

References
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4. Conclusions Some commercial surfactants used for the formation in microemulsion systems were able to com-