Separation and Purification Technology 33 (2003) 115 /126 www.elsevier.

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Analysis of polarized layer resistance during ultraltration of PEG-6000: an approach based on ltration theory
Chiranjib Bhattacharjee *, Siddhartha Datta
Department of Chemical Engineering, Jadavpur University, Calcutta 700 032, India Received 25 December 2001; received in revised form 23 July 2002; accepted 23 July 2002

Abstract A mathematical model based on filtration theory, coupled with resistance in series model and gel polarization/film model has been developed in the present study. Unlike the cake filtration equipment where cake deposition continues until the wash cycle comes, in case of continuous stirred ultrafiltration the deposited solutes are allowed to build up over the membrane indefinitely, along with continuous back transport of deposited solutes into bulk by the turbulence created by stirring action. To account for this back transport, a coefficient called back transport coefficient has been defined which is found to be independent of any operating variables. Variation of polarized layer resistance was also studied with different operating variables like bulk concentration, stirrer speed and pressure differential. A correlation was also developed relating polarized layer resistance with those operating variables. A comparative study has been made between experimentally found polarized layer resistance value, using ultrafiltration data of Bhattacharjee and Bhattacharya, with those found from correlation and this developed model based on filtration theory. The model has been found to predict the polarized layer resistance reasonably well once the three parameters describing the model viz. permeability coefficient, back transport coefficient and membrane hydraulic resistance are known along with the operating condition. Using the above-mentioned parameters, it is also possible to predict flux and/or total permeate volume at any time under a given operating condition. # 2003 Published by Elsevier B.V.
Keywords: Polarized layer; Ultraltration; Filtration theory; Flux; Film theory

Nomenclature A transport area (m2) a constant in Eq. (13), defined by Eqs. (14)/(16)) b constant in Eq. (21) c concentration (kg/m3) cb bulk concentration cp permeate concentration
* Corresponding author E-mail address: c_bhatta@hotmail.com (C. Bhattacharjee). 1383-5866/03/$ - see front matter # 2003 Published by Elsevier B.V. PII: S 1 3 8 3 - 5 8 6 6 ( 0 2 ) 0 0 1 4 2 - 9

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cg D J K kb M MWCO P DP Pm PEG r Rm Rp Rp,expt Rp,corr Rp,calc Sa t V z Greek letters a o m v p v

membrane surface/gel concentration diffusivity (m2/s) volumetric permeate flux (m3/m2 s) mass transfer coefficient (m/s); calculated by Eq. (5) back transport coefficient (m3); defined in Eq. (3) molecular weight, kg/kmol molecular weight cut off pressure (N/m2) pressure difference permeability coefficient (m2); defined in Eq. (1) poly ethylene glycol radius of the membrane (m) membrane hydraulic resistance (m (1) polarized layer resistance (m (1) experimental value correlation value calculated from present model surface area per unit particle volume (m (1) time (s) total permeate volume collected up to time t (m3) thickness of deposited solute layer (m)

specific cake resistance (m/kg) void fraction, dimensionless viscosity (kg/m s) angular velocity (rad/s) density (kg/m3) kinematic viscosity (m2/s)

1. Introduction During the last few decades ultrafiltration has been considered as promising technology to solve many separation problem in various industries like pulp and paper, food processing, pharmaceuticals, paints, etc. However, the growth of the technology has fallen far behind the initial anticipation. One of the major obstacles, which hinder more widespread application of ultrafiltration, is that the flux declines with time [1 /4]. This phenomenon is commonly termed as membrane fouling. It reduces the production rate and increases complexity of membrane filtration operation since the system has to be stopped frequently to restore

the flux by back flushing. This phenomenon also results in difficulty regarding the simulation of permeate flux and rejection at any operating condition. In the past two or three decades substantial experimental effort has been made to investigate effects of various parameters on flux decline and mechanisms of membrane fouling. While data of time dependent fluxes have been collected from numerous ultrafiltration experiments under various conditions, not much progress has been made in understanding of the fundamental mechanisms of membrane fouling. This results in difficulty regarding the theoretical prediction of flux and rejection in such separation process.

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Various attempts have so far been made regarding the theoretical modeling of the fouling phenomenon and hence thereby predicting flux and rejection as a function of time. Trettin and Doshi [5] developed their theory essentially based on gel layer formation and proposed their integral model which was an effort in the unification of macromolecular ultrafiltration theories with classical filtration theory. This model differentiates substantially compared to the Shen and Probstein [6] model. Experiments with unstirred batch cell using BSA solution were performed to testify this model [7]. A summary of governing transport and adsorption phenomenon in porous membrane ducts under isothermal condition was given in the review article by Belfort and Nagata [8]. The development of mathematical models has provided a conceptual framework for understanding the phenomenon responsible for flux decline. Most of the equations used to characterize ultrafiltration systems are extrapolations of models previously developed for other filtration systems. For example, the osmotic pressure model was originally developed for reverse osmosis membranes [9], while resistance models are very similar to those used in classical filtration [10]. On the other hand the gel model was specifically developed for the ultrafiltration of macromolecules [11]. Recently, all the reported works regarding the simulation of an ultrafiltration process are all based on any one of these three models or any combination of that. Some models are very good with respect to particular solute/membrane combination but it may lack accuracy while predicting for other systems. Various works on the simulation of an ultrafiltration process have been reported in literature recently. Simulation of an ultrafiltration process has been discussed by Secchi et al. [12] and Minnikanti et al. [13]. Mechanism and modeling of the membrane fouling dynamics has been reported by Song [14]. A computer simulation was discussed by Lebrun et al. [15] to calculate the membrane performance data for a rectangular slit configuration. A very good work in formulating the concentration polarization phenomenon was reported by Song and Elimelech [16]. The model applies to concentration polarization of non-

interacting particles in cross-flow filtration system. A significant work regarding modeling of concentration polarization and depolarization with high frequency back pulsing was reported by Redkar et al. [17]. In this study, a turbulent back transport of rejected solutes has been assumed from the deposited layer (termed as gel layer) to the bulk by the action of stirring. True gel can form only when the membrane surface concentration exceeds the solubility limit of the solutes in the solvent. It is reported [18] that in case of poly ethylene glycol (PEG)-6000, filtration with ultrafiltration (UF) membrane of 5000 molecular weight cut off (MWCO), membrane surface concentration never exceeds this solubility limit. So this deposited layer is not a true gel layer but may be called a gel type layer whose properties are supposed to be the same as that of cake in filtration equipment. The membrane continuously rejects the solutes and the thickness of this deposited gel layer will thus increase. But at the same time, due to action of stirring, some solutes are removed from the cake surface and go into the bulk. Due to this action, increase of thickness and hence resistance of deposited layer to permeate flow gets somewhat reduced than that it would be in case of unstirred filtration. The concentration in the deposited layer called gel concentration was found by using two different models */the first one is the gel polarization model and the second approach is from steady state solution of governing partial differential equation obtained from unsteady state film model. The back transport rate due to stirring is assumed to be proportional to gel concentration and stirrer velocity. Kozeney / Carman equation was used to relate the permeate flux with other operating variables. So this work is a combination of filtration theory and gel polarization model/film model. Experimental data of Bhattacharjee and Bhattacharya [18,22] were used to fit this model and to find the values of different parameters, namely back transport coefficient, permeability coefficient and membrane hydraulic resistance. Once these three parameters are known total amount of permeate collected up to any desired time under a given set of operating condition can be computed.

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2. Theory At the beginning of the continuous stirred UF process, the boundary layer first forms over the membrane and it was shown in many previous literatures that this layer actually develops within a very short period of time, in most cases within 1 s. After the development of concentration boundary layer, the flux decline occurs mainly due to the build up of some extra resistance caused by deposition of solute over the membrane. It was reported in many previous studies that membrane surface concentration for PEG-6000 solutes never exceeds the theoretical limit for gel concentration which was set by solubility value of PEG-6000 in water at the specified temperature and pressure. In fact it is reportedthatwaterandPEGaresolubleineachother irrespective of any concentration limitation. So it has been proposed that instead of a true gel layer, a gel type layer called polarized layer has formed within which the concentration remains constant at the membrane surface concentration value predicted from concentration polarization model and film model. This extra layer offers the polarized layer resistance, which is responsible for flux decline during the initial period of continuous stirred UF. The behaviour of this gel layer is supposed to be similar to those of cake in conventional filtration. It may be assumed that the flow of filtrate through the deposited gel type layer is laminar. By laminar flow, it is meant that the type of flow in which the pressure drop is proportional to first power of fluid velocity. The Hagen /Poiseuille equation could be used in this case since the filtrate is flowing in laminar flow through passages in the bed. However, although the bed resistance is proportional to the thickness of the layer, characteristic of the deposited layer such as size and shape of the particles and fraction of void volume in the polarized layer will also affect this value. Therefore it is not possible to use simple Poiseuille equation. The most accepted equation in this field was the Kozeny /Carman equation: dV dt 0A  o3
2 o(1 ( o)2 So

Pm 0

o3 1 0 2 2 o(1 ( o) So rs a(1 ( o)

(2)

While doing the overall mass balance over the system, it has been assumed that total solute rejected by the membrane results in partly raising the concentration in the so called gel-type polarized layer over that of the bulk and remainder being transported back into bulk by convection current created by stirring action. It has been further assumed that back transport rate is proportional to the stirrer speed and gel concentration. Then the overall mass balance equation can be written as follows: V (cb (cp )0Az(cg (cb )'kb cg vt; z0 V   cb ( cp ( kb cg vt or (3)

A cg ( ch

A cg ( cb

2.1. Determination of gel concentration Gel concentration was determined based on two different approaches:

2.1.1. Gel polarization model Concentration polarization model can be expressed mathematically as follows: J0/k ln [(cg(/ cp)/(cb(/cp)], which can be solved for cg to give: cg 0cb '(cb (cp )eJ=k (4)

The mass transfer coefficient appearing in the previous equation can be computed from the wellknown empirical correlation [19], applicable for stirred cell: k 00:0443(D=r)(n=D)0:33 (vr2 =n)0:8 (5)



DPc mz

0 APm

  DPc mz

(1)

The viscosity and density of PEG-6000 in water solution can be related to polynomial function of concentration as suggested by Bhattacharjee and Bhattacharya [18]. Further, the diffusivity can be empirically related to the molecular weight of polymer solution [20]: D0 2:74)109 M 1=3 (6)

where Pm is the permeability coefficient with

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2.1.2. Film model with osmotic pressure effect Unsteady state mass balance over the film of thickness d gives @c @c @2c 0J 'D @t @x @x2 (7)

Adding membrane resistance in above equation to replace pressure drop across the cake (DPc) by overall pressure drop (DP ), one can get according to resistance-in-series model, J0 1 dV DP 0 A dt m(Rm ' z=Pm ) (10)

Though this equation was derived under condition of constant density, the dependence of density on concentration was allowed in further analysis [18,22]. The ultrafiltrate volumetric flux can be defined by J 0(D=(c(cp ) @c @x for x 00

Above equation can be rearranged to give, 1 J 0 mRm DP ' mz Pm DP (11)

Substitution of z from Eq. (3) gives: 1 J (8) or, 1 0 a1 V (a2 t'a3 J where, a1 0 a2 0 a3 0 m(cb ( cp ) Pm DPA(cg ( cb ) mkb cg v Pm DPA(cg ( cb ) mRm DP (14) (15) (16) (13) 0 mRm DP Pm DP     V cb ( cp k cg ( b vt A cg ( cb A cg ( cb ' m

So Eq. (7) becomes,   @c @2c D @c @c 0D ( 2 @t @x c ( cp @x x00 @x

(12)

Above partial differential equation was solved by finite difference method with following initial and boundary conditions: t00; c0 cb for all x @c (c ( cp )(DP ( Dp) x0 0; 0( for all tc0 @x mDRm x0 d; c0cb for all tc0 Osmotic pressure was related to PEG concentration in water by Florys equation. Solution of above partial differential equation provides concentration profile in the boundary layer as a function of time. Steady state concentration profile at x 0/0 gives the so-called gel concentration which in most cases was found to be higher than the value obtained from Eq. (4). The above technique was reported in detail by Bhattacharjee and Bhattacharya [18].

2.2. Formulation of relevant equations If Eq. (1) is compared with general form of rate equation as suggested by Darcys law, it will be noted that the term z /Pm corresponds to the resistance term because Eq. (1) can be rewritten as, J0 1 dV DPc 0 A dt m(z=Pm ) (9)

Using experimental data of Bhattacharjee and Bhattacharya [18], the gel concentration cg can be determined for each experimental run under different operating conditions by any of the two methods described earlier. After finding the value of cg, Eq. (13) may be used for each experimental run with V and t as independent variable and 1/J as dependent variable, for determination of unknown parameter a1, a2 and a3. Eq. (13) represents a linear over-determined system problem. This can be solved by the method of least square. An equation of the form y0 ani ai xi 'ani'1 ; with ni i01 number of independent variables (here ni 0/2), can be reduced to a set of simultaneous linear algebraic equation of order (ni'/1). This final set of

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equation may be solved by gauss elimination to find the desired unknown coefficients ai s [21]. Another alternative is to use experimentally determined value of membrane hydraulic resistance. If, Rm determined by water run is known, then Eq. (12) can be rearranged as 1 J ( mRm DP 0a1 V (a2 t (17)

The total permeate volume collected up to time t may also be obtained by numerically integrating the following integral:
t

V 0A

gJ
0

calc (t)dt

(19)

with only two unknown parameters a1 and a2 as given by Eqs. (14) and (15). The left hand side of Eq. (17) is the dependent variable which may be fitted against the two independent variable V and t. Obviously, first method gives prediction of Rm along with Pm and kb, and is recommended only when Rm is unknown. With known values of Rm substituted as in Eq. (17), the latter method gives slightly less deviation in terms of prediction of Rp, J and V . The coefficients determined in the manner vary from experiment to experiment due to change in operating condition [the ai s are function of DP , cb and v according to Eqs. (14) /(16). Once these values are known, the unknowns Pm, kb and Rm may be determined from Eqs. (14) /(16), respectively. These parameters are characteristics of the membrane separation system under a constant temperature and pressure and with same solute membrane combination. So an average value of all the three parameters determined from all the experiments may be used as the desired value of membrane permeability coefficient (Pm), bulk transport coefficient (kb) and membrane hydraulic resistance (Rm). Once the values for above three parameters have been obtained the polarized layer resistance may be calculated from the following equation obtained by combining Eqs. (3) and (9):   V cb ( cp k cg Rp;calc 0 vt ( b P m A cg ( cb P m A cg ( cb 0z=Pm (18) and it may be compared with the experimental value. Also the permeate flux may be determined from Jcalc 0 DP m(Rm ' Rp;calc ) (18a)

To calculate V at any time t, from above equation, J was calculated at equispaced time interval and then Simpsons 1/3rd rule has been used to evaluate the above integral.

3. Experimental [18,22] A continuous stirred cell has been used for the purpose of experimentation. Flat disc, asymmetric, hydrophilic cellulose acetate membrane of MWCO 5000 was used in conjunction with highly porous polymeric support. The diameter of the membrane was 76 mm with effective filtration area 2.64 )/ 10(3 m2 and that of stirrer impeller was 56 mm. Solution of PEG-6000 were prepared using distilled water. The details regarding the levels of bulk concentration, pressure difference and stirrer speed, along with the experimental values of observed rejection are shown in Table 1. The concentration of PEG-6000 in the feed and in permeate were measured by refractive index calibration method. Details of the experimental methods, characteristic of membrane and the UF cell were reported elsewhere [18,22].

4. Results and discussion In this study, the experimental data were taken from the work of Bhattacharjee and Bhattacharya [18,22]. The gel concentration corresponding to any experimental run for a specific operating condition can be obtained by two methods as described earlier. The values obtained by the two methods differ significantly and in almost all the cases, gel concentration calculated by film model with osmotic pressure effect was found higher than that calculated by gel polarization model. The differences between these two values are higher at

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Table 1 Expt No. Pressure difference, DP (kPa) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 827 827 827 690 690 690 552 552 552 827 827 827 690 690 690 552 552 552 827 827 827 690 690 690 552 552 552 Stirred speed, v (rad/s) 55.5 47 34 55.5 47 34 55.5 47 34 55.5 47 34 55.5 47 34 55.5 47 34 55.5 47 34 55.5 47 34 55.5 47 34 Bulk concentratioin, cb (kg/m3) 20 20 20 20 20 20 20 20 20 50 50 50 50 50 50 50 50 50 70 70 70 70 70 70 70 70 70 Rejection, Ro 0/(1(/cp/cb) 0.67 0.85 0.80 0.76 0.88 0.77 0.91 0.83 0.82 0.74 0.74 0.65 0.75 0.80 0.66 0.91 0.92 0.82 0.71 0.68 0.63 0.72 0.71 0.61 0.79 0.69 0.67

low bulk concentration and gradually their differences become narrowed at higher bulk concentration. Once the gel concentration has been obtained, its variation with different parameters can be studied. Fig. 1 shows the variation of gel concentration calculated by two methods with applied pressure differential and stirrer speed at a fixed value of bulk concentration. The figure shows that with increase in stirrer speed, the gel concentration drops as shown by continuous line if the other conditions remain unchanged. With the increase in stirrer speed the back transport rate increases which leads to the removal of deposited solutes from the membrane into the bulk. This is much more pronounced at the lower bulk concentration because of high cg/cb ratio which prevails at low bulk concentration. So increase in stirrer speed reduces the membrane surface concentration due to increased turbulent back transport, which in

turn is responsible for the decrease of the polarized layer resistance in the process. Eq. (13) was fitted by multivariable regression as mentioned before for each experimental run at different time points. The constant a1, a2 and a3 were found by this method for each experiment under different operating conditions. The dependent variable, which was fitted in this analysis, was 1/J . In the calculation, any gel concentration value obtained by the two different methods may be used. But it was found that use of gel concentration value obtained by film model with osmotic pressure effect gives less deviation in terms of prediction of Rp, V or J. The average absolute deviation in the prediction of Rp was 16.8% with cg calculated by gel polarization model, whereas the same with cg calculated by film model with osmotic pressure effect, gives 9.3% deviation (3parameter model, as will be discussed latter). Due

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The experimentally determined value of Rm was 1.978 )/1013 m (1, which means an error of 7.6%. If this value of Rm was used in Eq. (17) and multivariable regression was performed to determine two remaining constants, the value so obtained were as follows: Pm 0/0.56 )/10(17 m2 and kb 0/0.135 )/10(10 m3. The experimental value of polarized layer resistance Rp,expt may be calculated from following equation: Rp;expt 0 DP mJ (Rm (20)

In the above equation, experimental values of J , DP , m , Rm are to be used. The membrane hydraulic resistance was calculated by passing pure water through the membrane [18]. It has been found that this polarized layer resistance varies with three operating variables cb, DP and v as well as time. A correlation has been attempted in this study to relate all these parameters. A multivariable regression in logarithmic form is attempted to relate all these variables with Rp. The final correlation equation obtained was as follows: Rp;corr 0b1 (cb )b2 (v)b3 (DP)b4 (t)b5 (21)

Fig. 1. Variation of gel concentration, calculated by two approaches, with pressure differential and stirrer speed at xed bulk concentration.

to this reason, cg calculated by latter method will be used in reporting various effects on Rp, V or J. The average absolute deviation of all the experimental run during the prediction of 1/J either from Eq. (13) or Eq. (17) by using coefficients determined by multivariable regression was found to be 0.056%. Such a low value of absolute deviation shows the goodness of fit of the experimental results by this model. The parameters Pm, kb and Rm were obtained from the determined constant value for each experiment and were found to be nearly constant. The average of all values were used as the desired parameter value which are given below: Pm 0/0.2838 )/10(16 m2, kb 0/ 0.1307 )/10(10 m3 and Rm 0/2.128 )/1013 m (1.

where b1 0/3.52668 )/1016, b2 0/(/0.065866, b3 0/ (/1.685281, b4 0/(/0.164592 and b5 0/0.057805. Above equation is dimensional and SI unit for all variables is to be used. The average absolute deviation in the variable ln(Rp,expt) was found to be 0.998% and for the corresponding value of Rp,corr was 12%. Considering the fact that polarized layer resistance is of the order of 1013 in m (1, this deviation was well within the limit. Three polarized resistance values i.e. experimental (calculated from Eq. (20)); correlation from Eq. (21) and the present model from Eq. (18) */all can be plotted on a single graph for a particular experimental run and was shown in Fig. 2(b). This figure shows the variation of polarized layer resistance as a function of time for an experimental run at constant cb, DP and v . The polarized layer resistance increases sharply to very high value within a short span of time. This is evident from three graphs corresponding to Rp calculated by different methods mentioned above. After a very sharp increase during initial period, this increase

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Fig. 2. (a) Variation of steady-state polarized layer resistance with trans-membrane pressure at constant bulk concentration and stirrer speed. (b) Polarized layer resistance as a function of time for a particular run.

becomes sluggish and gradually approaches an asymptotic value within a time of 2/3 h. Average absolute deviation in the prediction of Rp was 9.3% using three parameter (Pm, kb, Rm) model, whereas it is 7.1% with two parameter (Pm, kb) model. Correlation values showed both positive and negative deviation but the model shows mainly negative deviation, though less than that of the correlation, which means that it has slight tendency to under predict Rp. This nature of prediction may be accounted due to rapid fouling and pore clogging of the membrane, which may be present in the initial period of an UF process. Variation of steady state polarized layer resistance as a function of trans-membrane pressure at constant bulk concentration and stirrer speed is

shown in Fig. 2(a). Here experimentally calculated values of Rp first increases and then decreases with DP . High pressure gives more flux due to increased driving force, which results in more accumulation of retained solutes and hence increase in gel polarized layer resistance. This is true for all solutes of nonpolymeric form. But PEG6000 is a polymeric macromolecule, whose entangled structure may get oriented in the direction of pore with the increase in pressure differential and may therefore pass through it. So here the shape of the molecule plays an important role in deciding rejection values. In fact this hypothesis was corroborated by the fact that rejection of PEG-6000 was found to decrease with increase in pressure [22]. So high pressure results in more

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passage of PEG molecule through the membrane which results in decrease in Rp at high pressure. Developed correlation in fact fails to accommodate this variation, though in any case deviation remains within bound. But the developed model has been found to be successful in predicting Rp as a function of pressure with the type of variation as mentioned before. Deviation was also found to be quite small as shown in figure. Fig. 3 shows the variation of steady-state polarized layer resistance with stirrer speed under constant DP and cb. With the increase in stirrer speed, the polarized layer resistance decreases as shown by three curves corresponding to Rp predicted by different methods-experimental, correlation and from present model. Increased stirrer speed causes more solute removal from the deposited layer to bulk by the action of turbulent back

transport mechanism. This also results in decreased gel concentration and hence lower polarized layer resistance. Fig. 4 shows the variation of steady state polarized layer resistance as a function of bulk concentration under constant stirrer speed and applied pressure differential. It shows that with the increase in bulk concentration, polarized layer resistance increases. As the bulk concentration increases, there will be more rejection of the retained solute, which will increase the thickness of the polarized layer, adding more resistance to solvent flow, thereby increasing the polarized layer resistance. Prediction of permeate flux and total volume collected by three parameter model, is shown in Fig. 5 for two experimental runs at different stirrer speed but at constant bulk concentration and pressure differential. The predic-

Fig. 3. Variation of steady-state polarized layer resistance with stirrer speed at constant trans-membrane pressure and bulk concentration.

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Fig. 4. Variation of steady-state polarized layer resistance as a function of bulk concentration at constant trans-membrane pressure and stirrer speed.

tion from two-parameter model is somewhat better than this, but not shown in the figure to keep the consistency about the fact that all results reported in every figure are for three-parameter model. This figure shows both the experimental results as well as those predicted from this model. Permeate flux was calculated from Eq. (18a) and cumulative volume from Eq. (19) by numerical integration method, as stated earlier. To calculate V at any time t, J was calculated from Eq. (18a) at 1 or 2 min interval and then Simpsons 1/3rd rule has been used to evaluate the value of V . The figure shows a very good fit for both flux and permeate volume. It also shows that J and V both should increase with increase of stirrer speed as expected, because increased turbulence will reduce polarized layer thickness due to more back transport of the rejected solute from polarized layer to the bulk and hence the resistance, Rp.

5. Conclusion An attempt to predict polarized layer resistance, and hence flux and permeate volume at any desired time, based on filtration theory, has been attempted in this study. One important parameter in the present model is the gel concentration, which has been found by two different methods. The well known gel polarization model could be used, but it results in somewhat higher deviation (16.8%) in case of the prediction of Rp and accordingly, the predicted results of flux and permeate volume are also not very good. But when cm was calculated by solution of film model with osmotic pressure effect, average absolute deviation reduces to 9.3% for three-parameter model, whereas it is 7.1% for two-parameter model. As a check, the predicted membrane hydraulic resistance from three-parameter model

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C. Bhattacharjee, S. Datta / Separation and Purification Technology 33 (2003) 115 /126 [2] M. Cheryan, Ultraltration Handbook, Technomic Publishing Company, Inc, 1986. [3] L.Z. Zeman, A.L. Zydney, Microltration and Ultraltration, Marcell Dekker, Inc, 1996. [4] E.S. Tarleton, R.J. Wakeman, Understanding ux decline in crossow microltration: part 1 */effects of particles and pore size, Trans. Chem. 71 (1993) 399 /410. [5] D.R. Trettin, M.R. Doshi, Limiting ux in ultraltration of macromolecular solutions, Chem. Eng. Commun. 4 (1980) 507. [6] J.S. Shen, R.F. Probstien, On the prediction of limiting ux in laminar ultraltration of macromolecular solution, Ind. Eng. Chem. Fundam. 16 (1977) 459. [7] D.R. Trettin, M.R. Doshi, Ultraltration in an unstirred batch cell, Ind. Eng. Chem. Fundam. 19 (1980) 189. [8] G. Belfort, N. Nagata, Fluid mechanics and cross ow ltration: some thought, Desalination 53 (1985) 57. [9] R.L. Goldsmith, Macromolecular ultraltration with microporous membranes, Ind. Eng. Chem. Fundam. 10 (1971) 13. [10] B.F. Ruth, Studies in ltration: derivation of general ltration equations, Ind. Eng. Chem. 27 (6) (1935) 708. [11] S. Nakao, T. Nomura, S. Kimura, Characteristics of macromolecular gel layer formed on ultraltration tubular membrane, AIChE J. 25 (1979) 615. [12] A.R. Secchi, K. Wada, I.C. Tessaro, Simulation of an ultraltration process of bovine serum albumin in hollowber membrane, J. Membrane Sci. 160 (1999) 255 /265. [13] V.S. Minnikanti, S. Dasgupta, S. De, Prediction of mass transfer coefcient with suction for turbulent ow in cross ow ultraltration, J. Membrane Sci. 157 (1999) 227 /239. [14] Linafa Song, Flux decline in crossow microltration: mechanisms and modeling of membrane fouling, J. Membrane Sci. 139 (1998) 183 /200. [15] R.E. Lebrun, C.R. Bonchard, A.L. Rollin, T. Masura, S. Sourirajan, Chem. Eng. Sci. 44 (2) (1989) 313. [16] L. Song, M. Elimelech, Theory of concentration polarization in cross ow ltration, J. Chem. Soc. Faraday Trans. 91 (19) (1995) 3389. [17] S. Redkar, V. Kuberkar, R.H. Davis, Modeling of concentration polarization and depolarization with high frequency back pulsing, J. Membrane Sci. 121 (1996) 229. [18] C. Bhattacharjee, P.K. Bhattacharya, Flux decline analysis in ultraltration of Kraft black liquor, J. Membrane Sci. 82 (1993) 1. [19] Q.T. Nguyen, P. Aptel, J. Neel, Characterization of ultraltration membranes. Part II. Mass Transport measurements for low and high molecular weight synthetic polymers in water solution, J. Membrane Sci. 7 (1980) 141. [20] T.K. Sherwood, R.L. Pigford, C.R. Wilke, Mass Transfer, McGraw Hill Inc, New York, 1975. [21] Francis Scheid, Numerical analysis, in: Schaums Outline Series, 2nd ed., McGraw Hill Book Company, 1989. [22] C. Bhattacharjee, M. Tech Thesis, IIT Kanpur, India, 1991.

Fig. 5. Variation of ux (J ) and total permeate volume (V ) with time at constant bulk concentration (cb 0/20 kg/m3) and pressure differential (DP0/690 kPa), but at different stirrer speed.

was compared with experimentally determined value and the corresponding deviation was found to be 7.6%. Results from correlation are reported here side by side along with experimental values and prediction from present model for comparison purpose. All the reported results show good fit of the proposed model to experimental data and prove its utility in the prediction purpose during continuous stirred UF of macromolecular solutes.

References
[1] G.R.H. Belfort Davis, A.L. Zydney, The behavior of suspensions and macromolecular solutions in cross-low microltration, J. Membrane Sci. 96 (1994) 1 /58.