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Journal of Membrane Science 134 (1997) 101-108

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Bench-scale membrane degumming of crude vegetable oil: Process optimization
L. Lin, K.C. Rhee, S.S. Koseoglu*
Food Protein Research and Development Center, Texas A&M University, College Station, TX 77843-2476, USA Received 10 December 1996; received in revised form 14 April 1997; accepted 14 April 1997

Abstract

Crude vegetable oils contain various minor substances such as phospholipids, coloring pigments, and free fatty acids (FFA) that may affect the quality of the finished oil. Reduction of energy costs and waste disposal are major concerns for many oil refiners who are looking for alternative methods to improve conventional refining methods, and during the last decade, energyefficient membrane separation technology has evolved dramatically. This paper reports the cross-flow bench-scale crude vegetable oil membrane degumming test results using newly available, modified, hexane-resistant, high flux, and high selectivity non-aqueous membranes. Two membranes (DS-7 and AN03) were evaluated for their flux and rejection properties. Process parameters including pressure, temperature, feed velocity and volumetric concentration factor were examined. A 99.6% rejection of phospholipids and a flux of 26.8 1/m2 h were achieved at pressure 300 psi, temperature 40°C, and feed velocity 2201/h using DS-7 membrane, and significant reduction of coloring pigments was observed as well. Membrane fouling presented no big problem. Keywords: Non-aqueous separations; Vegetable oil; Degumming; Phospholipids; Foods

I. Introduction

1.1. Chemical composition of crude vegetable oil Crude vegetable oils are obtained mainly by crushing oilseeds, followed by solvent extraction. Approximately 6.9 x 109 kg of crude oil is processed each year in the US [ 1]. Triacyleglycerols constitute over 95% of crude vegetable oils; the remaining components include phospholipids, free fatty acids (FFAs), pigments, sterols, carbohydrates, proteins, and their *Corresponding author. Tel.:+l 409 845 2749; fax: +1 409 845 2744; e-mail: s-koseoglu@tamu.edu. 0376-7388/97/$17.00 © 1997 Elsevier Science B.V. All rights reserved. Pll S0376-7388(97)00098-7

degradation products [2]. These substances may impart undesirable flavor and color, and shorten the shelf-life of oil. Thus, crude vegetable oils undergo complex refining processes to achieve the desired quality. 1.2. Conventional refining process of crude vegetable oils The conventional refining operation consists of four steps. The first step is degumming to remove the phospholipids. Next, FFAs are neutralized with sodium hydroxide (NaOH) to produce soaps, which are then removed with remaining phospholipids by

The energy usage can range from 4600 to 9300 KJ for each kilogram of finished oil. 2). . the basic principles of edible oil refining have not changed in the last 70 years [4]. Commercial membrane applications in the food industry include waste water treatment. The potential energy savings from the implementation of this technology in the US alone is estimated to be 15-22 trillion KJ per year [1]. Accordingly. large amounts of energy are consumed to heat and cool the oil as well as to provide power to pumps. Performance of membrane separation is affected by membrane composition.102 L. and in addition. oils and other materials [5]. and (3) reduce waste water production. If the energy savings are combined with other savings. have a molecular weight of 20 000 or more [7]. such as reduced capital investment. Although improvements have been made in process engineering and equipment design. triacylglyceroles and phospholipids have similar molecular weights (about 900 D). ketones and other volatile compounds [2]. solid waste and heavily polluted effluents are produced. phospholipids can be separated from triacylglyceroles in the miscella stage by using appropriate membranes. Membrane separation in crude vegetable oil refining The practical use of membrane separation began in the 1960s with desalination of sea water [5]. the oil is steam distilled under high vacuum to strip out trace amounts of FFAs. and Non-aqueous NonFolar bydrophobe N Insoluble foreign bodies Fig. Lin et al. 1). The pigments are then adsorbed by acid-activated bleaching clays. H~O or . depending upon the age of the facility. form reverse micelles in a non-aqueous environment with globular structure (Fig. The majority of the coloring materials and some of the FFAs and other impurities are included in the phospholipid micelles and removed as well. fruit and vegetable juice processing. However phospholipids are surfactants in nature. Theoretically. The membrane-based crude oil degumming produces permeate and retentate fractions containing triacylglyceroles and phospholipids. Micelle Invertedmic~'lle ~ ~ Aqueous Polar hydrophil ~ ~0 IZ:Z3 ~ or SwollenmiceHes ~O ? ~ hexane 1. loss of neutral oil with gums can be reduced by 75% [8]./Journal of Membrane Science 134 (1997) 101-108 centrifugation. Membrane separation is primarily a size-exclusionbased pressure-driven process. l. which contain 25-30% of crude oil and 70-75% of hexane. It separates different components according to the molecular weights or particle sizes and shapes of individual components. fractionation and purification. pressure. which are thus lost [3]. In addition. The micelles formed. they have both hydrophilic and hydrophobic ends. which makes them difficult to be separated by a membrane.3. Micelle formation in both aqueous and non-aqueous environments [1]. are obtained from oil extraction prior to solvent removal. Neutral oils constitute about 25-40% of the soapstocks and phospholipid gums. During oil processing. (2) reduce energy consumption. temperature.°=. aldehydes. Since then this energy-efficient separation technology has been widely applied to the food processing area for the purpose of low cost concentration. Finally. miscella. velocity of flow and interactions between components of the feedstock and with the membrane surface. dairy products processing and recovery and purification of proteins. Thus membrane technology can be applied to edible oil refining to (1) simplify the whole process. centrifuges and other equipment. Due to the multi-step refining process. respectively (Fig. and is somewhat dependent on their interactions with the membrane surfaces and other components of the mixture [6].

Mechanismof membranedegumming. However. Lin et al. and to determine the separation efficiencies under various operating conditions. and the majority of the membranes evaluated either do not have the selectivity or reasonable flux necessary for commercializing this technology. M a t e r i a l s Cottonseed oil miscella were obtained by mixing 25% of crude cottonseed oil with industrial grade 15 ( ~ ) 14 N 13 2 7 8 1 5 12 1) 2) 3) 4) 5) 6) 7) 8) Feed Storage Tank Steam Jacket Air Mixer Control Valve Feed Feed Pump Pressure Gauge Thermometer 9) PressttreTransducer 10) UF Membrane 11) ControlValve 12) Permeate 13) Retentate 14) PressureGauge 15) ControlValve I Pressure Regulator Fig. and various membrane modules and membrane compositions [13-16] were evaluated to achieve high selectivity for phospholipids.L. waste reduction. Different additives [11] and surfactants [12] were added. Later. and recovery of neutral oil and phospholipids. precrystallization [9] and physical refining [10] was investigated. Apparatus and schemeof the cross-flowbench-topmembranesystem. 3. Development of membrane degumming of crude vegetable oils began in 1977 [3]. Materials and methods 2. the literature does not contain sufficient information on membrane degumming and the problems associated with membrane stability and membrane fouling/cleaning. a combination of ultrafiltration with silica gel percolation [7]. hexane-stable membranes have created great opportunities for applying membrane technology to crude vegetable oil refining. 2. . The purpose of this study was to test two newly available nonaqueous membranes for their flux and selectivity during membrane degumming.1. Some research has also been done on the removal of FFAs [17-19]. the total impact of this new technology to the whole edible oil industry can be doubled [8]./Journal of Membrane Science 134 (1997) 101-108 103 MicellePigments- PhosphoHpid t"Monomer Other Impurities -~etentate I --~Permeate [ Fig. Newly available. 2.

Factors affecting flux Permeate flux is a function of system-operating parameters and physical properties.6 2. Effects of operating parameters including pressure. Experiments The apparatus and scheme used for the bench-top cross-flow membrane degumming of cottonseed miscelia is shown in Fig. Minnetonka. x is membrane thickness. Increasing the temperature lowers the viscosity and increases the diffusivity and both effects increase the flux. Therefore there was no compaction of membrane at this pressure range. The hexane flux increased linearly when pressure increased from 100 to 400 psi. following a linear flux temperature model. r is membrane pore radius. The compaction and selectivity of membranes were tested.02674 m 2 was used.2. A flat-sheet membrane module with an effective area of 0. Table 1 Effects of membrane type on permeate flux and phospholipid rejection rate DS-7 Materials Thin film polymer 1000 22.4 94. The total phospholipid content was determined by multiplying phosphorus content by 30. CA) with a molecular weight cutoff (MWCO) of 1000. feed velocity. MWCO (Dalton) Permeate flux (1/m 2 h) Phospholipid rejection (%) membrane performance are mainly due to the different MWCO of the two membranes. 5). The literature indicates that the lower pressure region is the pressure-controlled region and the higher pressure region is the mass transfer-controlled region.1. DS-7 has a higher phospholipid rejection rate.4 AN03 Polyamide 15 000 49. One model used in membrane processing is j- 2. These differences in where J is permeate flux. Temperature: High flux rate was obtained when temperature increased (Fig. and volumetric concentration factor (VCF) on separation efficiency were evaluated by comparing permeate flux and phospholipid rejection rate. Results and discussion 3. It is due to the consolidated gel layer on the membrane surface that the pressure independence of flux was observed [6]. The high selectivity and flux result in high efficiency and short processing time. MN) with a MWCO of 15 000.1. the DS-7 membrane (Desalination Systems. 3.104 L. To avoid signifcant .2. ~7 is fluid viscosity. The FFA content was analyzed using AOCS method Ca5a-40 [20]. The DS-7 membrane was chosen for further study because of its higher phospholipid retention. erZp 8~Ax 3. Table 1 shows the characteristics of the two membranes employed and their effects on permeate flux and phospholipid rejection rate. Membrane selection The molecular weight cutoff of membranes. Chemical analysis The phosphorus content was measured using the AOCS method Ca12-55 [20]. Richmond. 3. Escodido. and e is membrane surface porosity [6]. which is defined as the smallest molecular weight species for which the membrane has more than 90% rejection. while its permeate flux is half of that of AN03.4 99. TX./Journal of Membrane Science 134 (1997) 101-108 hexane. Inc. Color was measured using the Lovibond tintometer [20]. 4... The cell was charged with 2. Pressure: Effects of pressure on hexane flux and miscella flux are shown in Fig. Crude cottonseed oil was provided by Southern Cotton Oil Co. temperature. and the SEPA-AN03 membrane (Osmonics. Two commercially available hexane-resistant membranes were employed. The miscella flux increased rapidly in the low pressure region and reached a steady state at pressure higher than 300 psi. Lin et al. P is transmembrane pressure.7 kg of the miscella.3. Inc. and were prefiltered before membrane degumming using microfiltration (100 p). plays a critical role in the maximum retention and permeate flux..

the temperatures chosen were below the boiling point of hexane (60°C). 20 = 5 10 o. 7). Volumetric Concentration Factor (VCF) is the ratio of the initial feed volume to the retentate volume.6 1. Volumetric concentration factor: Permeate flux decreased drastically with volumetric concentration factor (Fig. 35 30 100 25. 7. (Q) phospholipid rejection rate. 6.4 1. ao ~. 5.2 1. := o J= ~ 2 '~ _~ el ~. The permeate flux remained nearly constant after the cottonseed oil miscella were concentrated five times. -~ ~ o f. Major resistances to flux Membrane resistance: Membrane Resistance (RM) is easily determined by the resistance to flow observed . Feed velocity: Fig./Journal of Membrane Science 134 (1997) 101-108 80 70 100 4 I I • 105 100 90 . ) miscella flux. Turbulence produced by pumping the miscellar fluid has a major effect on flux.8 2 Average Trensmembrane Pressure (psi) Fig. The a value of the 25% cottonseed oil miscella is 0. Lin et al. ~" so ~ 70 _=a. The magnitude of the effect of feed velocity on flux follows the equation F l u x = C Velocity a. (O) phospholipid rejection rate. 20 10 0 5 2o ~ o f. ( I ) m i s c e l l a flux. 4. which indicates a turbulent flow. 0 2O 30 40 50 5 0 Temperature I(*C) 50 40 30 20 lO 0 ~ _~. Effectsof volumetric concentrationfactor on permeate flux and phospholipid rejection rate: ( . 100 190 A -i70 ¢ 20 90 g ~ ~ " 25 ~ 80 70 ~ 60 = 2o 15 60 ~ so ~" v K 15 o E 40 ~. Effects of feed velocity on permeate flux and phospholipid rejection rate: (m) miscella flux. by sweeping away the accumulated solutes and reducing the thickness of the boundary layer on membrane surface. Ln (Feed Velocity) Fig.~ 9o ~ ~" I= o ~ 6o 80 70 n. Fig. The increase of retentate viscosity and extensive fouling of membrane at high volumetric concentration factor led to the decrease of permeate flux.L. 0 1. 5O 40 30 oo so 40 30 20 10 0 0 100 200 300 400 60 ~ 50 40 o. 6). Effects o f t r a n s m e m b r a n e p r e s s u r e on p e r m e a t e flux and p h o s p h o l i p i d rejection rate: ( I ~ ) h e x a n e flux. (0) phospholipid rejection rate. Effects of temperature on permeate flux and phospholipid rejection rate: (m) miscella flux. 2 3 4 5 Volumetric Concentration Factor (VCF) Fig. and concentration indicates the degree of separation attained.70 (slope of Fig. 6 shows effects of feed velocity on permeate flux. vaporization of hexane during processing. 3.3. ( O ) p h o s p h o l i p i d rejection rate.

1685x + L.. Fouling resistance: A major limiting step in the use of pressure-driven membrane processes is fouling due to the accumulation and deposition of submicron particles on the membrane surface and/or the crystallization and precipitation of smaller solutes within the pores of membrane.2 0. 3.t. Membranes with large MWCO usually give low resistance. The RF of 0 indicates no fouling.5 (Feed Velocity}"a Fig.-I v _=it.17. 10.1463x + 5. Thus. Fouling decreased flux significantly during the first several hours of operation (Fig. and . Fig. The relationship between hexane flux and average transmembrane pressure before degumming and after cleaning: ( 0 ) hexane flux before degumming.64. Concentration polarization has a significant contribution to the total resistance. respectively. 10 shows the relationship between ATP/Flux and Feed Velocity -a.1 0. RF = 2. 5 200 300 400 0 2 4 6 J 8 Average Transmembrane Pressure (psi) Time (hr) Fig. | 20 10 0 f 100 = 0. resulting in a lower filtration rate at constant pressure [21].3 0./Journal of Membrane Science 134 (1997) 101-108 . As shown in Fig. the Rp value was 6. (11) hexane flux after cleaning. Lin et al. and the RF of this system was 2. al A ~A 30 25 20 x 15 @ o a.ATP (RM + RF + Rp) Given flux = 26.31 LMH.106 70 60 50 40 30 y = 0. a further resistance to the flow is encountered [5]. 9. 12 with clean solvent [21]. Fig. RM = 0. Extrapolation to infinite velocity gives the RF value. Polarization Resistance (Rp) is a variable which increases as filtration proceeds. 9).4 0.15. Polarization resistance: Concentration polarization arises when the rejected compounds tend to form fairly viscous and gelatinous-type layers on the membrane.4.64. temperature. the RM of DS-7 membrane before degumming and after cleaning was 0. Fouling Resistance (RF) is a useful parameter to compare various membranes. calculated from [22]: 1 1 Flux . 8.17 and 0. It can be 10 8 6 4 2 0 0 0. Factors affecting retentivity of membranes The retentivity of a membrane mainly depends on membrane type. o a. The decay of permeate flux with operation time during total recycle. There was no significant fouling in this system.9584 _= t. It is the slope of the plot of clean hexane flux versus Average Transmembrane Pressure (ATP). There was no significant change in membrane properties during operation. The relationship between ATP/Flux and Feed Velocity ".69 at 250 psi. 8. molecular size of solutes and microenvironmental conditions like pH.

1989. aMembrane: DS-7. CA. feed velocities. Academic Press. and oil distributions after membrane separation are summarized in Table 2. 1989. Koseoglu. Engelgau. Conclusions The results in this study indicate that membrane separation is effective for removing phospholipids and other impurities from crude cottonseed oil. Oils and Fats International.0R-40Y 3. Patent 44093540 (1978).K. and feed velocity 220 1/h.S. Membrane degumming has been shown to be effective in various crude vegetable oils with different phospholipid contents. [6] M.5. Most pigments were entrapped in phospholipid micelle and were concentrated into the retentate. temperature 40°C. temperatures.7 33. respectively. Linet al..74 Color of permeate oil 2.0 4. Lancaster. similar results with cottonseed oil were obtained. Gupta. Membrane Application and Research in Food Processing. [3] A. No significant disruption of micelle structure was observed under different pressures.S.8 1/m 2 h and phospholipid rejection rate over 99% were achieved from DS-7 membrane at pressure 300 psi. Use of membrane technology in edible oil processing: Current status and future prospects (unpublished). .S. Hoffman. Charboneau. and FFA distributions in membrane-processed cottonseed oil Oil (%) Crude oil Permeate oil Retentate oil 100 65 35 Phospholipids (%) 100. Figs.6 [1] S.E. [4] S. and its retentate were 10. Inc. and reduction in yellow color (Y) was also achieved. Koseoglu and D. 4-7 show that a 99100% phospholipid rejection rate was maintained in all trials. Engelgau. free fatty acids. 2. 4. The phospholipid. Color measurements of crude cottonseed oil.78 31. Other effects of membrane separation on crude cottonseed oil Color in oil results from pigments remaining in the oil. San Diego. Purification process.K. temperature: 40°C. U. [8] S. Membrane applications and research in the edible oil industry: An assessment. References 3. Similar results were obtained using other crude vegetable oils.0R-71Y. U. Mohr.E. J.0R-30Y 3.A.D.56 98. feed velocity: 2201/h. Reduction in red color (R) in permeate oil was significant.2 FFAs (%) 100.. No concentration reduction of FFAs in permeate oil was achieved. and deodorization operations. [2] G.S. All phospholipids existed in micelle forms above their Critical Micelle Concentration (CMC).6 95.L. D. NJ. Soc.0 65. phospholipid. A comparison Table 2 Oil. Membrane degumming of crude rice bran oil When this technology was applied to crude rice bran oil. 67 (1990) 239-249. 1986. About 35% of the oil remained in the retentate at a concentration factor of 5. Patent 4062882 (1977). Process for refining crude glyceride oils by membrane filtration.0R-79Y. Park Ridge. and volumetric concentration factors. S. Table 3 Comparisons of membrane degumming of crude cottonseed oil and crude rice bran oila Permeate flux (LMH) Cottonseed oil Rice bran oil 26. Ultrafiltration Handbook. Gupta. [5] C. Oil Chem. The permeate flux of 26. [7] A. Am. Leeper and B.54 Phospholipid rejection rate (%) 99.S./Journal of Membrane Science 134 (1997) 101-108 107 concentration of solutes.L. bleaching. Cheryan. Koseoglu. its permeate.0R30Y and 28.M. with good potential for energy savings. Noyes Data Corp.. Membrane technology for edible oil refining. A pilot plant study is underway and further investigation to increase selectivity of membranes will be conducted in our lab. pressure: 300psi. Technomic Publishing Company.S.S. This oil could be recovered by increasing the concentration factor or using a continuous system.6. The Chemistry and Technology of Edible Oils and Fats. Red color is usually the most significant criterion in refining. some of which might be removed by bleaching. The requirements for absorbents for further bleaching were greatly reduced. between membrane degumming in crude cottonseed oil and that in crude rice bran oil is listed in Table 3. 5 (1991) 16-21. PA.

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