Separation and Purication Technology 16 (1999) 8393

Oil removal from oil-in-water emulsions using PVDF membranes

J. Kong, K. Li. *
Chemical Engineering Department, National University of Singapore, 10 Kent Ridge Cresent, Singapore 119260, Singapore Received 5 May 1998; received in revised form 2 September 1998; accepted 21 September 1998

Abstract A microporous hydrophobic membrane allows the permeation of an oil phase at almost zero pressure and retains the water. The separation of dilute oil-in-water mixtures using at sheet hydrophobic PVDF membranes has been investigated using an unstirred laboratory scale semi-batch experimental system operated at 40C. The at sheet membranes were prepared in the laboratory by an immersion precipitation method and were characterised in terms of a mean pore radius, porosity and breakthrough pressure. The oil-in-water mixture contains 1% kerosene in distilled water. The experimental work essentially entails the study of the eects of various system parameters on the oil/water separation characteristics. In particular, the eects of feed ow rate, the operating pressure and pore size and porosity of the membrane were studied. The experimental results can be predicted reasonably well using the HagenPoiseuille equation at a high vertical velocity and the percentage of oil removed can be achieved as high as 77% under normal experimental conditions. 1999 Elsevier Science B.V. All rights reserved. Keywords: Microporous poly(vinylidene uoride) membranes; Oil/water separation; Phase inversion

1. Introduction Membrane technology at the present time is extensively applied in many sectors of the manufacturing industry, including gas separation and enrichment, water desalination, ultra-pure water production, production of beverages, product recycling and recovering, emission control and pollution abatement. In the last category of applications mentioned above, membranes have been successfully applied or considered as likely candidates for treating liquid waste from food processing, metal fabricating and plating, mining, textile
* Corresponding author. Tel: +65 874 6388; Fax: +65 779 1936; e-mail: chekangl@nus.edu.sg

and photograph products. Many of these wastes are aqueous solutions, others are mixtures of liquids which are immiscible or only partially miscible. Many investigations attempted the use of ultraltration membranes for treating oily wastewater in the past [111]. The membranes used were either polymeric ones such as cellulose acetate, polysulfone or polyethersulfone or inorganic ones such as alumina and glass with a molecular weight cut-o of 20,00050,000. As these membranse were quite hydrophilic and have relatively small pores, water which was free of oil or with reduced oil content were recovered as permeate. For wastewater with 0.1%10% of oil content, product water with less than 10100 ppm of oil was obtained [2].

1383-5866/99/$ see front matter 1999 Elsevier Science B.V. All rights reserved. PII: S1 3 8 3- 5 8 66 ( 9 8 ) 0 01 1 4 -2

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Use of membranes for treating oily wastewater is usually operated in semi-batch with continuous withdrawal of the permeate and recycling of the oil-enriched non-permeate. It has been suggested [1] that the ow rate of the wastewater to be treated should be kept suciently high so those agglomerated oil molecules may be entrained by liquid ow and not retained at the membrane surfaces. With reduced membrane pore blockage and membrane fouling, a relatively high water ux may be obtained. As the oil content of most oil/water mixtures to be treated is low, using ultraltration membranes of a hydrophilic type for their treatment requires the recovery of relatively large quantities of permeate. In turn, this means a large membrane area requirement (or in semi-batch operation, a relatively lengthy period of operation) and high-energy consumption. Intuitively, it would be logical to treat oil/water mixtures by using hydrophobic membranes. With hydrophobic membranes, oil may be produced as a permeate. In other words, both membrane surface area and energy requirements may be signicantly reduced, thus making the operation more economically appealing. In the present study, we report our investigations on the removal of oil from a dilute oil-in-water emulsion using hydrophobic PVDF membranes of dierent pore sizes and porosities. The membranes were prepared in our laboratory, using a phase inversion technique. The objectives were to investigate the membrane properties and operating conditions which would permit some control of the permeate quality and quantity and hence the extent of oil separation from oil-in-water emulsion, based on the preferential wetting principle.

2. Background A few instances of using hydrophobic membranes to recover oil phase as a permeate are found in the literature [1218]. Unno et al. [12] studied the use of PTFE (polytetrauroethylene) membranes for separating oil from oil/water mixtures by using a stirrer system. Two types of PTFE membranes, stretched and porous with pore sizes 110 mm, were used. These investigators hypothes-

ised that separation of oil takes place by a series of three steps: (i) attachment of oil droplets to the membrane surfaces on the upstream side; (ii) penetration of oil into and through the membrane; and (iii) release of oil droplets from the membrane surface of the permeate side. The experimental results suggest that the rate is controlled by steps (i) and (iii), as well as oil viscosity. In a subsequent study, Ueyama et al. [14] reported the results of treating oil/water emulsions using a microporous PTFE at sheet membrane with a pore size of 0.67 mm. Batch experiments were conducted and the variables examined included the fraction of oil of the emulsion, the agitation speed in the emulsion phase and the presence of surfactant in the emulsion. Of the last variable, it was found that the oil permeation ux drastically declined as the surfactant concentration reached a critical concentration. Daiminger et al. [16 ] reported results on the use of hydrophobic membranes for separating oil/water mixtures. They applied both hydrophobic PTFE and polypropylene membranes in their study. The PTFE membrane (with a pore size of 5.0 mm) was used as an oil coalescer and the hollow bre polypropylene membrane modules were used to obtain an enriched oil droplet suspension as a permeate. These invesigators concluded that the extent of separation was determined by the residence time of the emulsions in the polypropylene membrane modules. More recently, Tirmizi et al. [18] used hollow bre membranes to demulsify oil/water emulsions. Both hydrophobic and hydrophilic membranes were employed in their study. Hydrophobic membranes having a pore size of 0.020.2 mm were tested for demulsication of water-in-oil emulsion and water/oil/solid mixtures. Their results indicate that, in the absence of surfactants, permeation of oil does take place and organics in wash water could be recovered using the hydrophobic membranes. Based on the above-mentioned studies, it appears that separation of oil/water mixtures by hydrophobic membranes with an oil-riched mixture as a permeate is indeed viable. However, hydrophobicity is just one of the variables which requires consideration in designing membrane sys-

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tems. Water may not penetrate through a hydrophobic membrane due to the presence of a nite wetting pressure acting along the direction opposite to that of penetration. Penetration of water through membranes, however, becomes possible if the applied pressure exceeds the wetting pressure. The wetting pressure of water can be described by the Laplace equation: P = w 2s cos h r (1)

where s is the interfacial tension (oil/water), h is the contact angle and r is the capillary (or pore) radius. As can be seen from Eq. (1), increasing the pore size of the membrane will decrease the wetting pressure of water, P . When the operating w pressure across the membrane is greater than the wetting pressure of water, permeation of water becomes possible and this will result in a decrease of the oil content in the permeate. The synthesis of an optimum hydrophobic membrane, therefore, requires a trade-o among a number of factors.

3. Experimental 3.1. Membrane preparation and characterization Membrane material, i.e. polyvinylidene uoride (PVDF, KynarA K-720) was purchased from Elf Autochem North America Inc.. N,NDimethylformamide (DMF ) and dimethylacetamide (DMAc) purchased from Merck were used as solvents, both of which are synthesis grade. Polyethylene glycol (PEG), with an average molecular weight of 400 or 15|000, respectively, was employed as an additive in the casting solution, in order to obtain desired membrane pore size for separation. The PVDF pellets were dried in an oven at 70C for 12 h before use. Dierent polymer casting solutions consisting of PVDF pellets, solvent (either DMF or DMAc) and non-solvent (PEG) were prepared. The solution was kept in an oven at 70C for several days until the polymer pellets were dissolved completely. Finally, the polymer solution was degassed at room temperature. The

compositions of the polymer solutions prepared are given in Table 1. The membranes were prepared by the immersion precipitation method. The polymer solution was cast on a glass plate at 20C, with relative humidity at 65%, and with a casting knife having a gap of 0.23 mm. Before casting, the glass plate and the casting knife were cleaned with acetone. The cast lms were exposed in the air for 30 s. Then, the glass plate with the thin lm was immersed into a water coagulation bath at 20C. After the lm completely detached from the plate, the precipitated membrane was removed from the coagulation bath to a tray containing fresh water (changed regularly), in order to remove the residual solvent and the additive. After stabilising for 3 days, the membranes were removed from the tray and dried in air at room temperature. The prepared membranes were characterised with maximum pore size, mean pore size and pore size distribution using a CA Porometer II, manufactured by Coulter Electronics Ltd. A typical plot of the pore size distribution curve is shown in Fig. 1. Porosity of the dried membranes was obtained using a method described elsewhere [19], while breakthrough pressures of the PVDF membranes were obtained by pressurising water through the membrane in air. All the measured membrane properties are also given in Table 1, along with other pertinent data. 3.2. Oil/water separation experiments The experimental apparatus for oil/water separation is shown schematically in Fig. 2. It consists of a cylindrical jacketed vessel (100 mm in diameter and 210 mm in height), tted with a at sheet membrane at the vessel base. The membrane is supported by a porous metal plate (3.30 mm in thickness). The material of the vessel is acrylic and the maximum membrane area available in this apparatus is 95.0 cm2. A centrifugal pump was used to recycle the oil/water mixture. A channelling tube with the inner diameter of 35.7 mm was tted from the top of the vessel. A shower head with 13 holes of 1.0 mm in diameter was xed on the end of the tube to produce a jet of the feed mixture, which is directly perpendicularly sprayed towards

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Table 1 Properties of casting solution and resulting membranes for oil/water separation Membrane number 1 Casting solution (wt.%) Poly(vinylidene)ouride K-720 Solvent Polyethlene glycol (PEG) Membrane property Maximum pore diameter (mm) Mean pore diameter (mm) Porosity Breakthough pressure, bar (gauge) Note: M =the average molecular weight of PEG. w

15 81 (DMF ) 4 (M -400) w 0.24 0.10 0.72 2.30

15 83 (DMF ) 2 (M -15 000) w 0.50 0.34 0.83 1.10

18 74 (DMAc) 8 (M -15 000) w 0.97 0.52 0.86 0.55

Fig. 1. Pore size distribution of the No. 3 membrane.

the membrane. The distance between the shower head and the membrane is adjustable. The operating temperature was controlled using a temperature-regulating water bath, while the system pressure was maintained using a puried nitrogen gas cylinder. The oil-in-water emulsion, consisting of kerosene (97% purity, Fluka, Switzerland ) was made up to 1 wt.% in distilled water. The kerosene was added to water and an emulsion was generated by mixing in a blender ( Waring Model 04244-77) at high shear rates for 2 min. The mixture (about 1.5 l ) was then poured into the separation vessel. The oil concentration in the vessel was determined using a total organic carbon analyser (Shimadzu 5000A) at 20 min intervals. Three samples were taken and measured at each interval and the average value is calculated to represent the concentration of oil in the vessel. 4. Results and discussion In order to analyse the factors that aect the oil permeation, mechanisms of oil transfer through the hydrophobic PVDF membranes must be identied. For the experimental set-up and the membrane employed in this study, the possible steps governing the permeation of oil through the membrane are: (1) oil droplets attach to the membrane because of the hydrophobic surface and the high velocity of the uid towards the membrane surface;

Fig. 2. Schematic diagram of the experimental apparatus.

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(2) oil droplets detach from the membrane surface due to the high uid velocity parallel to the membrane surface; (3) oil penetrates into the membrane pores due to the capillary force and operating pressure; and (4) oil releases from the membranes by sweeping with an inert gas. A schematic diagram demonstrating the physical picture of the oil permeation is shown in Fig. 3. From the above hypothesis, it is suggested that the oil permeation through the membrane depends not only on physiochemical properties of the membrane and oil, but also on the operating pressure, ow velocity of the feed and membrane pore size. In most cases, however, only one or two factors control the oil transfer. Therefore, in this study, the theoretical analyses of the velocity proles of the uid in the vessel are presented rst. The analysis of the experimental results is presented second and is focused on the eects of operating conditions such as pressures and uid velocities, and the membrane properties such as membrane pore sizes on the extent of oil separation. Finally, performance of the PVDF membrane for removal of oil from the oil-in-water emulsion is also evaluated. 4.1. Preliminary analysis of velocity proles of the uid As mentioned earlier, the velocity of the feed mixture towards the hydrophobic membrane surface is one of the most important process parameters in the oil/water separation. Current literature on studies involving oil/water separation using hydrophobic membranes has not provided comprehensive information on the uid velocity distri-

bution. For the experimental set-up used in this study, the important process parameter would also be the velocity distribution of the mixture as it leaves the channelling tube and ows over the membrane at the base of the vessel. Ignoring any rotational ow, both the perpendicular and lateral components of the uid velocity are required in order to estimate of the uid momentum near the membrane surface. Modelling the velocity distribution is not trivial, since, in addition to turbulent ow being prevalent in the system, the ow boundaries near the exit of the channelling tube are an intrinsic function of the system dimensions. Detailed information can be obtained using available software packages dealing with uid dynamics such as F, which is capable of solving turbulent ow processes. Some preliminary results were obtianed using F ( V4.32 obtained from Fluent Inc., USA). Fig. 4 shows the velocity distribution at the bottom of the separation vessel for an impervious surface (i.e. no spearation through the membrane). The values on the left side of Fig. 4 refer to the changes of the vertical uid velocity (m s1) from the shower head to the membrane. The solution was obtained for the system parameters (with water properties used for the uid) given in Table 2. The velocity prole shows a vertical velocity from the channeling tube towards the bottom surface, which eventually spreads outward. The diagram also shows the presence of reserve ow near the vessel wall, as expected. Fig. 5 shows the velocity prole near the stagnant surface. In this case, it is interesting to note that vertical velocity components towards the bottom surface are only signicant for the area

Fig. 3. Schematic diagram demonstrating the physical picture of oil transfer.

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Fig. 4. Simulation of uid velocity distribution in the separation vessel. Table 2 Systems parameters Vessel length (cm) Vessel diameter (cm) Channelling tube diameter (cm) Height between channelling tube and vessel bottom (cm) Inlet flow velocity (cm s1) 20 12 4 6 4

slightly larger than that of the inlet channeling tube. This may indicate that the eective membrane area available for the oil/water separation is dependent on the size of the inlet channeling tube, as described later. 4.2. Analysis of experimental results The amount of oil permeated through the membrane was measured at dierent operating condi-

tions. The values of permeation ux, J(t), m s1, were obtained from a second order polynomial t of a plot of V (t)/A (volume of kerosene in the k vessel, m3/membrane area, m2) vs t (operating time, s), followed by analytical dierentiation. The base operating conditions for all the experiments are given in Table 3, while the operating condition under study is specied in each individual gure. Figs. 6 and 7 show V (t)/A vs t for three dierent k PVDF membranes at dierent operating conditions. Table 4 shows typical values of the permeation ux, J(t) obtained from Fig. 6(a). Experimental results for dierent membranes and dierent operating conditions are presented in Figs. 810. In Fig. 8(a), the oil permeation ux, J(t) is plotted against the residual concentration of oil in the vessel, c(t), for dierent operating pressures, i.e. pressures at the membrane surface

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Fig. 5. Simulation of the velocity prole near the stagnant surface. Table 3 Base operating conditions for all the experiments Feed velocity (m s1) Shower height (mm) Membrane area (cm2) Pressure at membrane surface (psi) 1.94 11.2 10.18 0.22

which are the stimulation of the operating gauge pressure and the hydraulic pressure (height of the liquid in the vessel ). It can be seen that the permeation ux, J(t), is a function of both the residual oil concentration in the vessel and the operating pressure for a given membrane studied. These results may suggest that the permeation of the oil is not only governed by the bulk ow of the oil through the membrane pores, but is also dependent on the oil concentration in the

water. Higher concentrations of oil in the water result in more oil droplets attaching to the membrane surface, hence giving the higher permeation ux of the oil through the membrane. The maximum (or constant) permeation ux can be reached if the oil droplets cover all the available membrane areas due to either higher concentrations of oil in the water or a higher inlet velocity, which is discussed below. The eects of inlet ow velocity and shower height on the permeation ux are also shown in Fig. 8(b) and (c). As can be seen, the permeation ux is dependent on the inlet ow velocity, v, as well as the shower height, h. For a given membrane area, the number of pores available for transfer of oil through the membrane is xed. The amount of the oil droplets in the oil-in-water emulsion capable of attaching to the membrane surface is largely

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Fig. 7. Residual oil per unit membrane area in the vessel vs time at dierent: (a) membrane areas; and (b) shower heights.

Fig. 6. Residual oil per unit membrane area in the vessel vs time at dierent: (a) membrane pore size and porosity; (b) operating pressures; and (c) feed velocities.

sonably good agreement with the theoretically calculated value of 1.66106 m s1, obtained from the HagenPoiseuille equation, assuming that the tortuosity, t, of the membrane pores is equal to 4.0: J= eDpr2 8tmd (2)

dependent on the inlet ow velocity and shower height. The experimental results given in Fig. 8(b) indicate that, at the inlet ow velocity of 2.58 m s1, the oil permeation is nearly independent of the oil concentration in the vessel, C(t), indicating that all the membrane surface is covered by the oil droplets. On the other hand, when the shower height is increased, the vertical ow velocity, especially near the surface of the membrane, dramatically decreases, resulting in less oil droplets transferring to the membrane surface, hence the much reduced permeation ux, as shown in Fig. 8(c). In Fig. 8(b), the experimental data further shows that, at the feed velocity of 2.58 m s1, the permeation ux of the oil is equal to 1.10106~1.20106 m s1, which is in rea-

In Eq. (2), J is the permeation ux, e is the membrane porosity, Dp is the pressure drop across the membrane, r is the pore radius, u is the uid viscosity, t is the tortuosity of the membrane pores, and d is the membrane thickness. In Fig. 9, the eect of the residual concentration of oil in the vessel, c(t), on the oil permeation ux, J(t) is shown for the membranes with dierent pore size and porosity. Again, the permeation ux, J(t), is dependent on the residual oil concentration in the vessel, further conrming that the degree of the attachment of the oil droplets on the membrane surface plays a role. Fig. 9 further reveals that the permeation ux, J(t), improves as the pore size of the membrane is increased. This is expected as the permeation ux, J(t), due to the bulk ow increases quadratically with the membrane pore

J. Kong, K. Li. / Separation and Purication Technology 16 (1999) 8393 Table 4 Oil permeation data obtained from Fig. 6(a) Time (s) Membrane number Oil concentration C(t) (vol.%) 1 0 1200 2400 3600 4800 6000 7200 0.0125 0.0116 0.0108 0.0093 0.0089 0.0083 0.0076 2 0.0125 0.0116 0.0103 0.0090 0.0072 0.0064 0.0055 3 0.0125 0.0109 0.0089 0.0063 0.0050 0.0045 0.0043 Permeation flux J(t) (m s1) 1 1.41106 1.28106 1.15106 1.02106 8.87107 7.56107 6.25107 2 1.90106 1.75106 1.60106 1.45106 1.30106 1.15106 1.00106 3

91

3.21106 2.75106 2.29106 1.83106 1.37106 9.14107 4.54107

Fig. 9. Eect of residual oil permeation ux for the dierent membranes.

Fig. 10. Eect of residual oil concentration on permeation ow rate for dierent membrane areas.

Fig. 8. Eect of residual oil concentration on the oil permeation ux under dierent conditions: (a) operating pressures; (b) feed velocities; and (c) shower heights.

radius, according to the HagenPosiseuille equation, given in Eq. (2). In Fig. 10, the residual concentration of oil in

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the vessel, c(t), is plotted against the oil permeate ow rate, Q(t) for two dierent membrane areas of 10.18 and 50.24 cm2, respectively. The former is equal to the area of the shower head, while the latter is considerably higher. The experimental results reveal that the permeate ow rate, Q(t), obtained for these two dierent membrane areas are almost identical. The reason for such a result is quite conceivable as the vertical velocity towards the membrane surface is only signicant for the area slightly larger than that of the shower head as discussed in the proceeding section. Further increases in the physical membrane area would certainly result in little improvement on the permeate ow rate as, in this case, the eective membrane area available for the attachment of oil droplets is dependent on the size of the shower head instead of the actual membrane area. 4.3. Performance of oil/water separation Fig. 11 illustrates the performance of the experimental apparatus for oil removal from the oil-inwater emulsion. The oil depletion curves, dened as the concentration of oil in the vessel at time t, divided by the initial concentration of oil in the vessel, i.e. c(t)/c(0), was plotted against the operating time for the three membranes studied. As can be seen from the gure, the oil concentration in the vessel decreases as the operating time is increased. The experimental results have shown that the percentage of oil removal achieved can be

as high as 77%, indicating that, based on the preferential wetting principle, separation of oil as a permeate from an oil-in-water emulsion is possible and is preferred, as long as an appropriate membrane can be selected. Using such a technique for the separation of low content of oil in an oil/water mixture, the membrane surface area and energy requirement are signicantly reduced, thus making the separation more economically appealing.

5. Conclusions Flat sheet PVDF membranes with dierent pore sizes and porosities have been prepared and employed for oil removal from a dilute oil-inwater mixture. The permeation of the oil as a permeate was investigated experimentally in an unstirred laboratory semi-batch apparatus. The eects of various parameters on the separation results have been analysed. The experimental results obtained at high feed velocity show a reasonably good agreement with the theoretical calculation. In most cases, the permeation of the oil through the membrane is controlled by the degree of the attachment of the oil droplets on the membrane surface. The experimental results indicate that it is feasible to use such an apparatus to remove oil as a permeate from the oil-in-water emulsion, based on the preferential wetting principle. In this study, the percentage of oil removed can be as high as 77%. The experimental results further reveal that the shower height and head area, membrane pore size, and feed velocity, as well as the operating pressure, are the important parameters which aected separation results signicantly.

Acknowledgments The authors gratefully acknowledge the research funding (GR6456) provided by the Wheelabrator Water Technology (S) Ltd, Singapore. A research scholarship provided by the National University of Singapore to one of the authors, Jianfeng Kong, is also gratefully acknowledged.

Fig. 11. Performance of dierent membranes on the oil removal from an oil-in-water emulsion.

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