Refining of crude canola oil using PSA ultrafilteration membrane

Ali Rafea, Seyed Mohammad Ali Razavib, M. H. Haddad Khodaparast a,b Department of Food Science and Technology, Ferdowsi University of Mashhad (FUM), PO Box: 91775-1163, Mashhad, Iran (alirafe1400@yahoo.com) b Department of Food Science and Technology, Ferdowsi University of Mashhad (FUM), PO Box: 91775-1163, Mashhad, Iran (s.m.a.razavi@um.ac.ir)
a

ABSTRACT The aim of this paper was to study the behavior of spiral wound configuration of polysulfone amide (PSA) membrane with 20 kDa molecular weight cut off (MWCO) in pilot-plant scale equipment used for refining micella canola oil under different operating conditions. Refining process parameters including phospholipids (PLs), color and free fatty acids (FFAs) were determined to express retentions (R%) and ultrafiltration process performance parameters such as permeate flux, membrane fouling and hydraulic resistances were determined. The results showed that the permeate flux was decreased considerably with increasing process time, although it was increased by increasing temperature from 30 to 50C and transmembrane pressure from 1.5 to 2 bar. The irreversible fouling resistance (Rif) and percentage of fouling were decreased as the temperature or transmembrane pressure increased. The results showed that the concentration polarization resistance (Rrf) was much higher than other resistances; therefore reversible resistance had an important role in total hydraulic resistance. In this paper, the retention of PLs, FFAs and color was so interesting due to improving the efficiency of oil refining process. The percentage of retention of PLs and FFAs was increased by temperature and decreased by transmembrane pressure and time; however, there was no significant difference in removing color under different operating conditions.
Keywords: Membrane; PSA; Refining; Canola oil; rejection; Hydraulic resistance; phospholipids; color

1. INTRODUCTION

Oilseeds are the second major food supply sources after cereals in the world [Shariati & Ghazi, 2000]. Canola is one of the most important oilseed crops of the world, as its production over the last 10 years has grown much faster than any other source of vegetable oil [Shahidi, 1990]. It is now second only to soybean as the most important source of vegetable oil in the world. During the last 20 years, this crop has passed peanut, sunflower and, most recently, cottonseed in worldwide production. It contains approximately 40% oil and yields a meal containing about 38-43% protein [Raymer, 2002]. The ratio of linoleic to linolenic acid in canola oil is 2:1 and this is considered to be a well balanced ratio for nutrition. It is less in saturated FFAs than any other vegetable oil, making it a popular choice among consumers [Raymer, 2002]. Crude canola oil is obtained mainly by crushing canola seeds, followed by solvent extraction. Approximately, 20% of oil is extracted in the first stage and canola oil meal contained 2-3% oil. Crude vegetable oils are constituted mainly of triacylglycerols, but contain some minor components such as phospholipids (PLs), free fatty acids (FFAs), sterols, coloring pigments, proteins and oxidation products, which would adversely affect the end-product and the processing efficiency [Padley, Gunstone, &,Harwood 1994]. These substances may impart undesirable flavor and color, and shorten the shelf-life of oil. Thus, crude vegetable oils undergo complex refining processes including degumming, neutralization, bleaching and deodorization to achieve the desired quality. Due to the multi-step refining process, large amounts of energy are consumed to heat and cool the oil as well as to provide power to pumps, centrifuges and other equipment. Neutral oils constitute about 25-40% of the soap stocks and phospholipids gums, which are thus lost [Gupta, 1977]. In addition, solid waste and heavily polluted effluents are produced. Although, some improvements have been made in process engineering and equipment design, the basic principles of edible oil refining have not changed in the last 70 years [Koseoglu, 1991]. As a result, the refining process has many drawbacks, such as high-energy demand, loss of neutral oil, use of large amounts of water and chemicals, heavily polluted effluents and loss of nutrients [Subramanian et al., 2001]. Membrane processes can be used in many areas of the vegetable oil industry. Some applications involving the extraction and refining of vegetable oils are now established for example, degumming while others are

still under development. These include solvent recovery by reverse osmosis (RO) or nanofiltration (NF), deacidification by NF, de-waxing by microfiltration (MF), recovery of hydrogenation catalysts by MF, nitrogen production for packaging applications by gas separation (GS), and wastewater treatment by MF, NF and RO. Performance of membrane separation is affected by membrane composition, temperature, pressure, velocity of flow and interactions between components of the feedstock and with the membrane surface. The application of membranes in edible oil refining has been investigated for their potential for energy savings as well as their potential for improvement in the oil quality [Subramanian et al., 2001], allowing combination of degumming and bleaching into a single step, thereby reducing energy requirements and making the use of chemicals unnecessary. In addition, membranes could play a role in the refining of mechanically extracted oil [Cuperus, 1999]. Phospholipids and triacylglycerols have similar molecular weights, about 700900Da, which makes them difficult to be separated by membrane. However, phospholipids are surfactants, having both hydrophobic and hydrophilic groups, and form reverse micelles in non-aqueous systems such as vegetable oils and oil/hexane miscella that enable their separation using appropriate membranes [Lin, Rhee, & Koseoglu, 1997]. Gupta (1977) reported that the molecular size of the miscella formed is about 20,000Da or more. In other words, miscella greatly increases the effective particle size of the phospholipids [Kim, Lee, & Tak, 2002]. It should be interesting to apply membrane technology immediately after the extraction stage, where the composition of oil/hexane miscella is usually found in the 1:3 range, which implies gains in terms of permeate flux, due to the lower viscosity of this solution compared to the desolventized crude oil. The membrane-based crude oil degumming produces permeate and retentate fractions containing triacylglyceroles and phospholipids, respectively. The majority of the coloring materials and some of the FFAs and other impurities are included in the phospholipids micelles and removed as well. As a matter of fact, oil refining could take advantage of emerging technologies such as membrane based processes. There are several papers dealing with ultrafiltration (UF) of miscella for solvent removing or for refining of vegetable oils [Sen Gupta, 1978; Koseoglu et al., 1989; Koseoglu and Engelgau, 1990; Raman et al., 1994]. Concerning the removal of FFA and PLS simultaneously, a few patents described dead-end microfiltration (MF) based refining of oils [Van de Sande, 1989]. Ceramic ultrafilteration membranes are also used for non-solvent sunflower oil degumming [Koris and Marki, 2006]. Recently, the development of hexane-resistant membranes have created opportunities for applying membrane technology to crude vegetable oil refining to simplify the whole process, reduce energy consumption and reduce wastewater production [Lin et al., 1997]. With regarding to, the non-aqueous systems such as oil-hexane-phospholipids have not enough information in the literature and the fastest growing separation technique in the food industry - the membrane-based separations; it is still interesting to study these systems. Therefore, the purpose of this study was to investigate polysulfone amide UF membrane for their flux and selectivity during membrane degumming of crude canola oil, and to determine the separation efficiency under various operating conditions. 2. MATERIALS & METHODS 2.1. Samples Canola oil miscella was prepared by mixing 25% (w/w) crude canola oil with 75 % (w/w) industrial grade hexane. Crude canola oil and hexane were supplied by Seh Gol Khorasn Co., Fazle Neyshabour, Iran. 2.2. UF operation Spiral wound configuration of polysulfone amide (PSA) membrane with an effective area of 0.03 m2 and a molecular weight cutoff (MWCO) of 20 kDa was used in these experiments (ARS-0.3, Biocon Company, Moscow, 1999). Experiments were performed in a cross-flow UF pilot-plant system equipped to stainlesssteel feed tank of 15 L, centrifugal pump, flow meter, UF module, two pressure gauges, tubular heat exchanger, digital thermometer and two control valves. [Rafe & Razavi, 2009]. Firstly, water and hexane fluxes of membrane are measured [Rafe & Razavi, 2009]. Canola oil miscella filtrations were performed at different operating conditions including transmembrane pressure at two levels of 1.5 & 2 bar, temperature at three levels of 30, 40 & 50 C, and process time at two levels of 15 & 30 min. Hexane flux after miscella ultrafiltration process is measured again to evaluate fouling of the membrane. The cleaning process was performed using alkaline and acidic detergents [Rafe & Razavi, 2009]. 2.3. Process performance parameters Evaluation of process performance of UF PSA membrane in refining crude canola oil is so important. Therefore, the following parameters were determined: Refining process performance parameters including

PLs, color and FFAs and UF process performance parameters including permeate flux, membrane fouling, hydraulic resistances, and rejections of phospholipids, color and other impurities. Percent of membrane fouling was obtained by replacing the values of hexane flux before and after miscella UF process in the following equation [Cheryan, 1998]: J h J fh (1) % Fouling = ( ) 100
Jh

Where, Jh and Jfh are flux of hexane before and after miscella filtrations, respectively. The inherent resistance of membrane (Rm, m-1) and total hydraulic resistance (RT, m-1) to permeate flux were calculated by applying the resistance-in-series model or boundary layer-adsorption model [Cheryan, 1998, Lin et al., 1997]. The total hydraulic resistance (RT, m-1) is sum of membrane hydraulic resistance and overall fouling resistance [Cheryan, 1998].The overall fouling resistance (RF) can be represented as the sum of the two components on the basis resistance-in-resistance model: resistance due to reversible fouling or concentration polarization (Rrf) and resistance due to irreversible fouling (Rif) [Cheryan, 1998]. The performance of the membrane process was also expressed in terms of the rejection of feed components. Miscella permeate samples were collected in regular time intervals in order to determine the removal percentage (%R) of phospholipids (PLs), free fatty acids (FFAs) and color pigments according to the following formula [Cheryan, 1998]:
%R = Cf Cp Cf 100

(2) Where, Cf and Cp were the concentration of each component in the feed and permeate streams, respectively. 2.4. Chemical analysis The phosphorus content was measured by the standard molybdenum blue, AOCS method Ca12-55 [Firestone, 1989]. The FFAs content was analyzed using AOCS method Ca5a-40 [Firestone, 1989]. Color was measured using the Lovibond tintometer method of AOCS Cc13e-92 by a glass cell with an optical path length of 10 mm [Firestone, 1989]. 2.5. Statistical analysis Three runs were performed with membrane under each experimental condition considered. All of the charts were prepared by Microsoft Excel software (2003). In addition, all of the regression equations and model validating parameters (correlation coefficient, R; coefficient of determination, R2, and adjusted R square, Adj. R2) were determined using Slidewrite software (version 2). 3. RESULTS & DISCUSSION 3.1. Ultrafiltration process performance 3.1.1. Permeate Flux The results showed that permeate flux was decreased considerably with increasing process time, and after almost 20 minute running, the flux reached to the stability position or the fluctuation was less. The preliminary time of process to access this stability is depend on the properties of feed solution, the characteristics of membrane and the conditions of operating process. It may be possible the transport occurs mainly by convection transport and partly due to solution-diffusion mechanism [Subramanian, 2001]. It can conclude from results that the permeate flux was increased by increasing temperature from 30 to 50C and transmembrane pressure from 1.5 to 2 bar. Furthermore, the miscella permeate flux was observed much lower than commercial hexane flux, because of probably higher viscosity of miscella and presence of fine particles of canola seed which were introduced to the oil during the extraction process. On the other hand, oil impurities particularly phospholipids may be increased hydraulic resistance and membrane fouling. The influence of pressure and temperature on average permeate flux under pseudo-steady state is presented in Figure 1. It can be seen that the permeate flux rose when the pressure increased from 1.5 to 2 bar, which is expected from Poiseuille-Hagen law, although the flux increasing was greater at higher temperature. The literature indicates that the lower pressure region is the pressure-controlled region and the higher pressure region is the mass transfer-controlled region [Cheryan, 1998].

Average flux, L/m .h

0 30 40 50

Temprature, C

Figure 1. Average permeate flux of canola miscella oil in pseudo-steady state as a function of temperature and TMP (, T=30C; , T=40C & U, T=50C)

3.1.2. Hydraulic resistances The results obtained for the hydraulic resistances are summarized in Table 1. The inherent membrane resistance was the slope of the curve of hexane flux versus TMP. The membrane resistance to fouling (Rm) was 1, 1.12 and 1.11 m-1 at temperatures 30, 40 and 50 C, respectively, and the average value of membrane resistance was obtained 1.079 m-1. It can also be found that the irreversible fouling resistance (Rif) and percent of fouling were decreased as the temperature increased from 30 to 50oC (Tables 1 & 2). It may be due to lowering the viscosity of canola oil, although the percent of fouling was still so high. By increasing transmembrane pressure, the irreversible fouling and percent of fouling was decreased a little due to the more impetus force and get farther the impurities of membrane. Perhaps, in order to have the more life of membrane, it is better as much as possible to operate in the high temperature and pressure. The results showed that the concentration polarization resistance (Rrf) was much higher than other resistances (about 50% of total resistance), therefore reversible resistance had an important role in total hydraulic resistance. In this research, the average of polarization resistance was obtained 2.35 m-1. By increasing TMP, total resistance (RT) was increased, whereas polarization resistance was lowered as pressure increased. Both of Rrf and RT were increased, when temperature increased from 30 to 50 oC.
Table 1. The hydraulic resistances of ultrafilteration of canola miscella oil under different operating conditions Temperature (oC) 30 40 50 Average Percent TMP (bar) 1.5 2.0 1.5 2.0 1.5 2.0 Rm (m-1) 0.98 1 1.12 1.10 1.11 1.09 1.079 22% Rif (m-1) 1.1 1.15 1.11 1.08 1.07 1.04 1.026 21% Rrf (m-1) 1.88 1.63 2.04 1.88 2.58 2.38 2.35 47% RT (m-1) 4.44 4.47 4.74 5.06 5.14 5.75 4.93 100%

The membrane fouling may be related to the much amount of fine particles in crude canola oil, membrane configuration as well as low MWCO of membrane. Fouling of membrane separation processes is good example where a minimum solidsurfactant interaction is preferred [Gupta and Muralidhara, 2001].
Table 2. Percent of membrane fouling during UF of canola miscella oil under different operating conditions Temperature (oC) TMP (bar) Fouling (%) 30 40 50 1.5 2.0 1.5 2.0 1.5 2.0 65.3 63.4 62.6 60.4 57.8 56.2

3.2. Refining performance parameters 3.2.1. Rejection of phospholipids The content of phosphorous of canola oil was approximately 527 ppm. As can be found that solvent oil extraction caused to introduce more phospholipids to oil, whereas pressed oil extraction had lower phospholipids. During the conventional degumming, the more content of phospholipids is removed, but its content did not approach to zero. Percent of phospholipids rejection by membrane is very interesting. Therefore, rejection of phospholipids during membrane filtration was determined, and the amount of phospholipids in permeate flux was measured at different operating conditions. The results are shown in the Table 3. Ultrafiltration process of canola miscella oil was showed high efficiency in removing phospholipids. As the temperature increases, rejection is decreased that may be due to dissolution of phospholipids or disruption micelle structure (Figure 2). Also, Percent of PLs rejection is increased as operation time and transmembrane pressure increased. The correlation between temperature, pressure and time on PLs rejection are given in the following equation and can be used for prediction of PLs rejection: %PL = 13.206 + (0.352 Temperature) - (2.503 Pressure) - (0.306 Time), R = 0.958, R2 = 0.917 The literature in the removing PLs from crude oil has shown its effectiveness. The amount of phospholipids in refined soy oil by UF membrane is shown effectiveness of this process in the other literature. By comparison between results can be found that UF process was removed approximately 99.6% [Lin et.al, 1997]. Some oils such as sunflower, rapeseed and cottonseed oil were completely degummed and can be directly refined by physical refining [Patterson, 1992].
100
100

Rejection phospholipids,%

Rejection phospholipids,%

99 98 97 96 95 94 93 92 91 90 30 40 50

99 98 97 96 95 94 93 92 91 90 30 40 50

Temprature, C

Temprature, C

Figure 2. Rejection of phospholipids (PLs) at different temperatures, Pressure 2 bar(left) Pressure 1.5 bar (right) (, t=15 min; , t=30 min)

Table 3 .Amount of phospholipids in the permeate flux at different operating conditions Temperature TMP Elapsed time Amount of phospholipids (C) (bar) (min) in permeate 15 15.81 1.5 30 10.5 30 15 13.7 2.0 30 9.5 15 19.6 1.5 30 13.2 40 15 16.8 2.0 30 15.7 15 24.1 1.5 30 16.8 50 15 20 2.0 30 16.8

3.2.2. Rejection of free fatty acids (FFAs) In spite of many investigation and trails have carried out for deacidification of edible oils (physical, chemical and biological methods), many difficulties still exist for removing free fatty acids from edible oils. Several researchers have also attempted the deacidification of vegetable oils with and without solvents, by using porous as well as nonporous membranes [Bhsole and Subramanian, 2004].

One of the main parameters in refining crude oil is the content of FFA. The more FFA content in oil caused more oil loss during refining process. As an example the oil has 1% FFA, oil loss was about 1 to 4%.so; decreasing FFA content is very important and economical factor in refining process. Crude canola oil has 1.36% FFA and its acidity was % 2.72. After membrane processing, the average %FFA was decreased to 0.8% and it means the free fatty acids has lowered 40% and by considering two percent oil loss during process, the total oil loss will be 1.6%. For achieving optimum conditions of UF process for removing FFA, percent of FFA rejection was measured, and can be seen in the Figure 3; by increasing temperature from 30 to 40C rejection of FFA was increased and then decreased. Percent of FFA rejection, as time and pressure progress was increased that may be possible due to the entrapment FFA in the PL micelles. The statistical analysis is shown that the optimum operating process to reach the proper flux by using 20 KDa PSA membranes was 40 C and 2 bar pressure. But for applying in industrial scale, the flux and time of process is low and need more investigation. The reason of low rejection of FFA in 50 C may be possible for preferential permeation that the FFA interlink to the micelle and could not be passed through membrane in this temperature.
60 55
55 54 53 52 51 50 49 48 47 46 45 30 40 50

Retention of FFA, %

35 30 25 20 15 10 30 40 50

T emprature, C

Retention of FFA, %

50 45 40

Temprature, C

Figure 3. Effect of temperature and process time on FFA rejection in 1.5 bar(left) and 2.0 bar(right) (, t=15 min; , t=30 min)

3.2.3. Color retention Canola oil is one of the more difficult oil in refining for having darker color and high content of chlorophyll, so, it needs more bleaching earth and therefore, impose more charge for refining. In the other word, the disposal of bleaching earth has the environmental difficulties. The lovibond has showed the color of crude canola oil 8.1R+85Y+5.2B, but canola miscella has 7.6R+74Y+3.5B color that it may be for adding solvent to oil and the color apparently decreased. By application membrane technology, color of canola oil was decreased as much as possible, but operating conditions have not the significant effect in color. Also, the statistical analysis has not showed significance effect. As can be shown the effect of pressure, time, temperature is not appreciable that may be due to entrapment of color pigment in micelles. Any way, color of miscella after UF treatment was decreased to 1.1R+22.4Y+0.1B. The presence of chlorophyll in crude edible oils, particularly, canola oil, is a difficulty in the process of refining oil and there are many drawbacks in the bleaching of oils [Bailey, 1985]. The literature showed that color improvement was occurred in the degumming and bleaching steps, but complete removal of chlorophyll is depend on conducting bleaching process. Furthermore, by using membrane degumming, bleaching is not so much necessary and neutralization has carry out rationally. CONCLUSION This study showed that membrane separation is effective in removing PLs, FFAs and increasing color quality particularly removing chlorophyll pigment in canola oil. Despite the promising results reported here, there is still a lot of work to be undertaken and phenomena responsible for the selectivity of the separation, mainly. For example these trials can be used for PES membrane which has the best efficiency for refining canola oil. REFERENCES
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