Desalination 245 (2009) 737742

A flux enhancing pretreatment for the ultrafiltration of acid whey

M.C. Almcija*, A. Guadix, A. Martinez-Ferez, P. Gonzlez-Tello, E.M. Guadix
Department of Chemical Engineering, University of Granada, 18071 Granada, Spain Tel. +34 958 243 308; Fax +34 958 248 992; email: mcalmeci@ugr.es
Received 30 June 2008; revised 03 February 2009; accepted 09 February 2009

Abstract The reduction in permeate flux caused by fouling is a drawback in the operation of membrane systems that can be alleviated using mechanical and electrical methods. Alternatively, physicochemical treatments provoking the elimination of fouling agents have been proposed as effective strategies for the enhancement of flux. A procedure (comprising salt addition, pH and temperature modification and centrifugation) that removes calcium and phosphate salts from acid whey without altering the profile of valuable proteins is presented in this research work. It has been demonstrated through the paper that this pretreatment enhances significantly the permeate flux of whey when cross-flow ultrafiltered through a 50 kDa tubular ceramic membrane both in total recycle and continuous diafiltration mode. For modelling purposes, a resistances in series model was applied to explain the effect of transmembrane pressure and a complete-standard blocking model fitted the experimental data of the variation of permeate flux with time. Keywords: Ultrafiltration; Acid whey; Ceramic membranes; Flux enhancement

1. Introduction Membrane fouling during whey filtration has been extensively studied in the scientific literature [1,2]. This undesirable phenomenon involves a reduction in permeate flux and, therefore, a lower productivity of the filtration process. In order to mitigate fouling, several strategies
*Corresponding author.

have been devised. Some mechanical methods [3] include: (a) turbulence promoters (such as baffles or moving balls) that reduce holdup in the feed channel by increasing velocities and wall shear rates; (b) periodic backflushing by pumping the permeate back to remove material absorbed onto the membrane; (c) uniform transmembrane pressure with a permeate pumping loop and (d) pulsatile flow obtained with pistons or rotating discs.

Presented at the conference Engineering with Membranes 2008; Membrane Processes: Development, Monitoring and Modelling From the Nano to the Macro Scale (EWM 2008), May 2528, 2008, Vale do Lobo, Algarve, Portugal.
0011-9164/09/$ See front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.desal.2009.02.045

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Other approaches apply an electrical field to a conventional membrane filtration unit, which is known as electrically-enhanced membrane filtration. Here, the electrical field acts as an additional driving force to the transmembrane pressure and reduces concentration polarisation. Brisson et al. [4] applied up to 3333 V/m during the microfiltration of whey protein solutions, where permeation was increased by a factor 3. Low frequency ultrasound has also been used to facilitate crossflow filtration of whey [5]. An enhancement factor of between 1.2 and 1.7 can be achieved at low irradiation power levels, which can be improved further with the combined use of turbulence promoters. Importantly, the membrane integrity is not altered by the ultrasonic irradiation, according to electron micrographs. Although proteins have been indicated as the main component of the fouling deposit formed during the processing of whey, calcium and phosphates have been also directly implicated due to the formation of insoluble calcium salts and as possible bridging agents between membrane and proteins or proteins themselves [6]. Therefore, precipitation processes involving the removal of calcium and phosphates, while preserving the protein composition, have been described for the palliation of membrane fouling. A simple procedure was proposed by Musale and Kulkarni [7] consisting of a pH raise to 7.5, 10 min holding at 28C and filtration through Whatman paper (No. 1). Kim et al. [8] (and posteriorly Rinn et al. [9] at a pilot plant scale) obtained clarified whey by cooling below 5C, adding CaCl2, adjusting to pH 7.3, warming to 50C and decanting/centrifuging the resulting precipitate. Gesan et al. [10] modified this pretreatment by increasing the temperature to 55C and maintaining the pH constant during the heat treatment. In this paper, a combination of these methods is presented with two main objectives: To maintain the original protein profile and to evaluate its capability of enhancing the permeate flux when whey is cross-flow

ultrafiltered with a 50 kDa tubular ceramic membrane.

2. Materials and methods 2.1. Obtention and pretreatment of whey Acid whey was obtained from pasteurized whole milk. First, the milk was centrifuged at 4C for 30 min in order to remove fat. Then, the pH was adjusted to 4.2 by adding 2 N HCl for casein coagulation, which was separated from the whey by further centrifugation at the same conditions. The pretreatment process applied to the acid whey was as follows: First, CaCl2 up to a concentration of 1.2 g/L was added to the whey at 25C. Then, pH was raised to 7.3 using 6 N NaOH and temperature was increased to 55C. These conditions were held for 8 min, involving the aggregation of complex lipidcalcium phosphate particles. Finally, the whey was cooled down to 10C and centrifuged for 30 min. The precipitate contained the insoluble calcium phosphate aggregates and the supernatant was the clarified whey. For both unpretreated and pretreated whey, individual protein concentrations (-lactalbumin, -lactoglobulin, BSA, lactoferrin and Ig-G) were determined by reversed-phase high-performance liquid chromatography (RP-HPLC) using the method described by Elgar et al. [11] and modified by Palmano and Elgar [12]. The HPLC system (Waters, Milford MA, USA) consisted of an Alliance Separation Module 2690 interfaced with a M-474 absorbance detector (214 nm) and a Millenium data acquisition and manipulation system. A 1-mL Resource RPC column (Amersham Biosciences, Uppsala, Sweden) was operated at room temperature at a flow-rate of 1 mL/min. Solvent A was 0.1% v/v trifluoroacetic acid (TFA) in MilliQ water and solvent B was 0.09 % v/v TFA, 90% v/v acetonitrile in Milli-Q water. The column was equilibrated in 80% solvent A. The gradient used was: 01 min, 20% B; 16 min, 2040% B; 616

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(a)

-LA -LG BSA IgG LF

0.99 g/L 3.07 g/L 0.12 g/L 0.39 g/L 0.04 g/L

(b)

-LA -LG BSA IgG LF

1.03 g/L 3.09 g/L 0.10 g/L 0.41 g/L 0.04 g/L

Fig. 1. Reverse phase HPLC chromatograms of unpretreated (a) and pretreated (b) whey. The concentration of the individual proteins is shown in the text box.

min, 4045% B; 1619 min, 4550% B; 1920 min, 50% B; 2023 min, 5070% B; 2324 min, 70100% B; 2425 min, 100% B; 2527 min, 10020% B; 2730 min, 20% B. 2.2. Ultrafiltration experiments In order to evaluate the influence of the pretreatment on the flux enhancement through ultrafiltration membranes, clarified acid whey and unpretreated acid whey were ultrafiltered

employing a 50 kDa tubular ceramic membrane (Tami, France). The pH of unpretreated whey was set at 7.3, which was the resulting value for the final pretreated whey. First, the influence of transmembrane pressure on permeate flux was analysed by operating the ultrafiltration rig in the total recycle mode at 30C, a cross-flow velocity of 3.5 m/s and transmembrane pressures between 0 and 2.5 bar. Permeate flux was calculated from mass measurements in an analytical balance.

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70 60 75 50 JF, L/(m2h) 0.5 1.0 1.5 2.0 2.5 40 30 20 10 0 0.0 0 0 1 2 t (h) 3 4

JF, L/(m2h)

50

25

P (bar)

Fig. 2. Permeate flux of unpretreated ( ) and pretreated ( ) whey as a function of transmembrane pressure at 30C for a 50 kDa tubular ceramic membrane.

Then, the time evolution of permeate flux was observed in the following operating conditions: temperature 30C, transmembrane pressure 1.5 bar and cross-flow velocity 3.5 m/s. The ultrafiltration mode was continuous diafiltration, which was conducted for 4 h with a constant retentate volume of 2 L. 3. Results and discussion With respect to a possible variation in the composition of individual proteins between the original acid whey and the pretreated one, according to the chromatograms depicted in Fig. 1, it can be concluded that no significant alterations were caused by the processing steps comprised in the clarification. Nearly identical concentrations were determined for the five proteins assayed. The correlation between permeate flux (JF) and transmembrane pressure (P) for both clarified and unclarified whey is shown in Fig. 2. It can be seen that permeate flow increased 3.03.5fold when the clarification procedure was employed, which demonstrates the applicability of the approach proposed. A linear relationship was obtained in both cases for transmembrane pressures up to 1 bar,

Fig. 3. Fluxtime profiles for the continuous diafiltration of unpretreated ( ) and pretreated ( ) whey at 30C for a 50 kDa tubular ceramic membrane. Transmembrane pressure was fixed at 1.5 bar.

which is usually referred as the pressure-controlled region. For higher pressures, a decreasing slope was observed due to the partial control of the mass transfer. This behaviour can be explained by the resistances in series model: P J = F a + b P (1)

where the parameter a takes into account the membrane and fouling resistances and b is involved in the computation of the polarisation layer resistance (which is considered to be proportional to the transmembrane pressure). The values of these parameters for the unpretreated (a = 6.13 102 bar m2 h/L, b = 1.24 102 m2 h/L, r2 = 0.999) and treated whey (a = 2.03 102 bar m2 h/L, b = 2.66 103 m2 h/L, r2 = 0.999) were employed to calculate the solid lines represented in Fig. 2. The results obtained for the parameter b reflect that a reduction in the resistance associated to the polarisation layer of 4.5 was achieved after the pretreatment. In Fig. 3, it is represented the time evolution of permeate flux when a transmembrane pressure of 1.5 bar was applied. During the continuous diafiltration, the fluxes droped from the initial

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Table 1 Fitting parameters of the complete-standard blocking model for the continuous diafiltration of unpretreated and treated whey at 30C through a 50 kDa tubular ceramic membrane

Unpretreated Treated 0.9691 0.8655

A (h1) 52.40 142.55

B (h1) 0.0953 0.2088

r2 0.9994 0.9980

values of 18 and 61 to the final 7 and 19 L/(m2 h) for unpretreated and pretreated whey, respectively. At the end of the 4 h of operation, only 0.9 diavolumes of unpretreated whey were filtered, while this amount was triplicated in the case of the pretreated one. In order to model the influence of the pretreatment in the time variation of flux, the experimental data were successfully fitted to a mathematical expression [13] combining complete blocking (provoked by particles arriving to the membrane that block some pores, without superposition, and responsible of a sharp decrease in flux at the beginning of the filtration) and standard blocking (caused by particles deposited onto the internal pore walls, which decrease the pore volume and explain a slighter flux drop during the rest of the operation): F = e A t + (1 ) J (1 + B t )2 F0 J (2)

amount of permeate flux is contributed only by the standard blocking term. Under these conditions, the value for unpretreated whey of the standard blocking parameter was responsible for a flux drop of 60%. Since the same parameter was doubled for pretreated whey, a higher decrease of 69% was achieved. In summary, although the pretreatment increased the kinetics parameters of fouling, an overall enhancement in flux was obtained due to the decrease in the fraction . 4. Conclusion A pretreatment procedure has been proposed for the clarification of acid whey in order to enhance the permeate flux through ceramic membranes. Its effectiveness was tested employing a 50 kDa tubular membrane in cross-flow operation. This process was able to remove fouling agents but did not affect the composition of individual proteins. As a result, when considering a transmembrane pressure range up to 2 bar, flux was improved by a factor of 3.03.5 with respect to the original whey, which could be related to a resistances in series model. With respect to the behaviour of pretreated whey under continuous diafiltration, the final volume of permeate collected after 4 h of operation was triplicated when compared to the unpretreated whey. The time evolution of flux was explained by a mathematical model combining complete and standard blocking. The fitting parameters showed that the pretreatment step provoked a decrease in the fraction of pores susceptible of being completely blocked but accelerated the fouling mechanisms.

where JF0 is the initial flux, is the fraction of pores susceptible of being completely blocked and A and B are the parameters of the complete and standard blocking, respectively. The values of these parameters are shown in Table 1. It can be seen that the removal of phosphate particles reduced one tenth the percentage of blockable pores from 97% to 87%. The high values obtained for the exponential parameters in the complete blocking term result in a fast kinetics for this process, in which the whole fraction of blockable pores was effectively blocked after 11 and 4 min of filtration for unpretreated and pretreated whey, respectively. After these times, the

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[7] D.A. Musale and S.S. Kulkarni, Effect of whey composition on ultrafiltration performance, J. Agr. Food Chem., 46 (1998) 47174722. [8] S.H. Kim, C.V. Morr, A. Seo and J.G. Surak, Effect of whey pretreatment on composition and functional properties of whey protein concentrate, J. Food Sci., 54 (1989) 2529. [9] J.C. Rinn, C.V. Morr, A. Seo and J.G. Surak, Evaluation of nine semi-pilot scale whey pretreatment modifications for producing whey protein concentrate, J. Food Sci., 55 (1990) 510515. [10] G. Gesan, G. Daufin, U. Merin, J.P. Labbe and A. Quemerais, Microfiltration performance: physicochemical aspects of whey pretreatment, J. Dairy Res., 62 (1995) 269279. [11] D.F. Elgar, C.S. Norris, J.S. Ayers, M. Pritchard, D.E. Otter and K.P. Palmano, Simultaneous separation and quantitation of the major bovine whey proteins including proteose peptone and caseinomacropeptide by reversed-phase high-performance liquid chromatography on polystyrenedivinylbenzene, J. Chromatogr. A, 878 (2000) 183196. [12] K.P. Palmano and D.F. Elgar, Detection and quantitation of lactoferrin in bovine whey samples by reversed-phase high-performance liquid chromatography on polystyrenedivinylbenzene, J. Chromatogr. A, 947 (2002) 307311. [13] E.J. de la Casa, A. Guadix, R. Ibez, F. Camacho and E.M. Guadix, A combined fouling model to describe the influence of the electrostatic environment on the cross-flow microfiltration of BSA, J. Membr. Sci., 318 (2008) 247254.

Acknowledgement This research work was funded by the Spanish Plan Nacional I+D+I under the Project CTQ2005-026/PPQ.

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