Separation and Purication Technology 26 (2002) 51 59 www.elsevier.

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Sieve mechanism of microltration separation

V. Starov a,*, D. Lloyd b, A. Filippov c, S. Glaser c
a

Department of Chemical Engineering, Loughborough Uni6ersity, Loughborough, Leicestershire LE11 3TU, UK b Department of Chemical Engineering, Uni6ersity of Texas at Austin, Austin, TX 78712 -1062, USA c Moscow State Uni6ersity of Food Industry, 11 Volokolamskoe sh., Moscow 125080, Russia

Abstract A theoretical model of dead-end microltration purication (MFP) of dilute suspensions is suggested. The model is based on a sieve mechanism of MFP and takes into account the probability of membrane pore blocking during MFP of dilute colloidal suspensions. An integro-differential equation (IDE) that includes both the membrane pore size and particle size distribution functions is deduced. According to the suggested model a similarity property is deduced, which allows one to predict the ux through the membrane as a function of time for any pressure and dilute concentration based on one experiment at a single pressure and concentration. For a narrow pore size distribution in which one pore diameter predominates (track-etched membranes), the IDE is solved analytically and the derived equation is in a good agreement with the measurements on four different track-etched membranes. A simple approximate solution of the IDE is deduced and that approximate solution as well as the similarity property of MFP process is in a good agreement with the measurements on a commercial Teon microltration membranes. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Microltration; Theory; Similarity property

Nomenclature D d f t c l S p n particle diameter pore diameter probability distribution function time concentration characteristic scale of pore and particle diameters membrane area probability number of particles

* Corresponding author. Fax: + 44-1509-223-923. E -mail addresses: v.m.starov@lboro.ac.uk (V. Starov), lloyd@chem.utexas.edu (D. Lloyd), a.lippov@mtu-net.ru (A. Filippov). 1383-5866/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 1 3 8 3 - 5 8 6 6 ( 0 1 ) 0 0 1 1 6 - 2

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V. Staro6 et al. / Separation /Purification Technology 26 (2002) 51 59

N J p L h m V a A k

number of pores ux pressure length of the pore membrane thickness porosity volume of liquid in the permeate see denition after Eq. (8) see denition after Eq. (4) permeability

Greek letters i parameter to characterise membrane pore inuence v viscosity l Dirac delta function see denitions after Eq. (8) ~ tortuosity k see denitions after Eq. (11) rejection coefcient Subscripts p m min max d 0 tr  *

particle membrane minimum value maximum value particles with diameter D B d initial value track-etched membrane at time tends to  specic value dimensional value

Superscripts * characteristic value ** after Eq. (10) according to mean value theorem

1. Introduction Microltration (MF) is widely used for the purication of colloid solutions having particles in the range 0.1 20 mm [1]. Distilled water often contains up to 100 000 such particles cm 3, but

for microelectronics processing this concentration should be less than 500 and in some cases not more than 2 particles cm 3 [2]. Thus, MF is useful for purication. During MF, the hydrodynamic resistance of the MF membrane increases (and water ux decreases) with time due to mem-

V. Staro6 et al. / Separation /Purification Technology 26 (2002) 51 59

53

brane pore blocking by particles from the feed solution and the formation of a foulant layer [1]. Existing experimental data and theoretical estimations show osmotic pressure inuences on MF are negligible compared with pore blocking and membrane fouling [3]. At high enough particle concentrations a layer of particles forms on the MF membrane [4], but at low concentrations it is possible to neglect this foulant layer formation and to consider only membrane pore blocking. Photomicrograph investigations show that even in the case of ultraltration of protein solutions it is possible to neglect protein molecules entering into membrane pores [5]. Consequently, it is possible to assume a sieve mechanism for MF of dilute solutions and to neglect particles deposition inside the membrane pores. The sieve mechanism can be described as follows: if the particle approaching the pore has a diameter less than the pore diameter, the particle goes through the pore. If the particle diameter is bigger than the pore diameter, the particle is retarded by the membrane, the pore is blocked, and the hydrodynamic resistance of the membrane is increased. The phrase approaching the pore, is dened in terms of a region of pore inuence. In this sense, if the pore diameter is d with a cross section yd 2/4, then all particles that are in the cylinder above the membrane with the bottom area iyd 2/4, where i (dened below) \ 1, either go through or block this particular pore depending on their diameter; if a particular particle is outside that cylinder, the pore under consideration does not inuence that particular particles behaviour (Fig. 1). The sieve mechanism of membrane pore blocking was introduced more than a decade ago [6], and there have been attempts to t selected functions to the time dependency of experimental ux data [7]. In such a procedure the physico-chemical meaning of tted parameters is not disclosed and there is no possibility of applying the resulting empirical equations to any other membrane or for different experimental conditions. Analyses of different membrane fouling mechanisms (sieve mechanism, foulant layer formation, etc.) is presented elsewhere [8,9]. Hubble [10] con-

siders MF separation of protein solutions in the framework of a two-parameter model of blocked and partially blocked membrane pores. It was assumed that the ratio of number of partially blocked pores and free pores is a linear function of the solution ux at the moment t. The ux decline in time was not considered. In a number of recent publications, the log-normal distribution of membrane pore diameters and the inuence of membrane fouling on that distribution are considered [11,12], but again ux decline with time and the dynamics of the pore size distribution in time were not considered. A number of models [13,14] were proposed for cake layer (or gel-layer) formation on the surface of membranes, which describe a ux decline with time. In Ref. [15] a model is proposed for a description of volume on time dependencies in microltration of suspensions, time series were predicted and coefcients were calculated and measured. A stochastic model of deep bed ltration has been suggested and elaborated [16,17]. In the following analysis, a similar model is used for MF with the additional consideration of taking into account both pores and particles probability distribution functions. In addition, a probability sieve model of dead-end MF proposed earlier [18] is extended and tested. The material below is organised as follows. First, a theoretical model is presented, an integro-differential equation (IDE) is deduced for

Fig. 1. Schematic presentation of the microltration process: 1, particle adheres to the membrane surface; 2, particle blocking a small pore; 3, small particle goes through a pore; and 4, particle will block the pore.

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V. Staro6 et al. / Separation /Purification Technology 26 (2002) 51 59

the ux-time dependency, and an exact solution of that IDE is obtained for the case of tracketched membranes. From examination of IDE, a similarity property is deduced and a simple approximate solution of the IDE is obtained. Second, experimental measurements on tracketched membranes and a commercial Teon membrane are presented and compared with the theoretical predictions.

2. Theoretical model In dead-end MF, the ow of the colloidal feed solution is normal to the membrane surface. All particle diameters D and membrane pore diameters d are made dimensionless as follows: D = D /l and d = d /l, where l is a characteristic length scale (Dmin or dmin, for example). The probability distribution functions of the particle diameters and membrane pore diameters are fp(D ) and fm(d ), respectively. Usually for MF purposes log-normal, bilog-normal, and Gaussian functions are used for the membrane pore diameter distribution function, fm(d ) [11,12]. Dmin, Dmax, dmin and dmax are minimum and maximum particle diameters (in the feed solution) and pore diameters, respectively. It is easy to show a low inuence of particle diffusion and concentration polarisation, which are neglected below. To derive the probability of pore blocking, consider a model membrane with only one pore with diameter ld. Then the probability that the centre of a random particle far from the membrane is projected into the pore area is the ratio of the pore area to the total membrane area; that is, y (ld )2/4S. Assuming that hydrodynamic and specic surface forces of interaction between the particle and the membrane pore result in an increase of the above probability by a factor i \ 1, that can be interpret as an increase of the effective pore area, the probability becomes iy (ld )2/4S. i is assumed below to be independent of the pore and particle sizes. To calculate the i value it is necessary to solve the hydrodynamic equation taking into account a local interaction in the vicinity of the membrane

pores (electrostatic, molecular, hydrodynamic, or other forces) for particles and membrane pores with all diameters under investigation. This is beyond of the scope of the present investigation. It is assumed below, according to the previous consideration and [18], that the probability of a single pore with diameter d being blocked by an approaching particle of diameter D \ d is equal to the ratio of the pore inuence area y (ld )2/4 to the total membrane area S (Fig. 1). If the particle diameter D B d, the particle goes through the pore into the permeate. Let n (d, t ) represent the number of particles of diameter D \ d that have approached the membrane surface during time t. Then the probability P (d, t ) of the event the xed pore with diameter d being not blocked at the time t is P (d, t ) = [1 iy (ld )2/4S ]n(d,t) (1)

To calculate the number of particles n (d, t ), the concentration cd of particles with diameters D \ d is determined. It is possible to conclude cd = c

&

Dmax

fm(x ) dx

where c is the particle concentration (number per cm3) in the feed solution. Diffusive ux is neglected; therefore, particles are transferred by convection only. The ux of particles with diameter D \ d is J (t )cd (where J (t ) is the solution ux) and the total number of particles n (d, t ) is an integral over time from that ux. That is n (d, t ) = cS

&

J (u ) du

&

Dmax

fp(x ) dx

(2)

Eqs. (1) and (2) allow one to simplify substantially the probability of pore blocking P (d, t ) because (i) the cross section of a single pore is much smaller than the membrane area, that is, y (ld )2/4  S ; and (ii) the number of particles approaching the membrane surface n (d, t ) is much greater than 1. Hence, from Eqs. (1) and (2) P (d, t )

= exp (yil 2d 2/4)

&

J (u ) du

&

Dmax

fp(x ) dx

n
(3)

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55

It is assumed below that the ow of the solution in each membrane pore is simple Poiseuille ow; that is, the local ux through the single pore with diameter d is yl 4d 4 Dp /(128vL ), where L is the length of the membrane pore, Dp is the applied pressure drop across the membrane, an v is the viscosity. For track-etched membranes L is equal to the membrane thickness h, but for other membranes L = ~h, where the tortuosity ~ accounts for deviation of the pore length from the membrane thickness. It is necessary to stress that the use of the Poiseuille equation is justied for track-etched membranes only, but it is seen below that the results obtained are for the most part independent of that assumption. After averaging all local uxes, the solution ux through the clean membrane (no pores blocked) J0 is obtained (this ux is referred to below as the initial ux at the moment t = 0): J0 = yNml 4 Dp /(128vLSA ) (4) where Nm/S is the number of pores per unit membrane area and A is dened as A=

&

The upper limit of integration is chosen as min(dmax, Dmax) because particles with diameters bigger than the maximum pore diameter dmax, can not go through the membrane pores, they can only block membrane pores. It is necessary to note that according to the suggested model the mechanism of particle rejection in MF is drastically different from that is reverse osmosis [19] and ultraltration. Fig. 1 attempts to clarify the mechanism of particle rejection in MF. Particles that adhere to the membrane surface and particles that block membrane pores are rejected; only particles in a region inuenced by a pore go through the pores if the particle diameter is smaller than the pore diameter. All those events are taken into account in Eq. (6). Eqs. (3), (5) and (6) show that MF can be fully described if the ux as a function of time, J (t ), is known. To deduce an equation for J (t ), Eq. (3) was substituted into Eq. (5) to yield the following integro-differential equation (IDE): J (t ) = J0A

dmax

x fm(x ) dx

d min

&

dmax

d min

The ux through the membrane at time t, taking into account pore blocking, is J (t ) = J0A

&

exp (yil 2c /4)x 2 fp(D ) dD dx

x 4fm(x )

&

J (u ) du

&

Dmax

dmax

x 4fm(x )P (x, t ) dx

(5)

d min

(7)

It is very important to notice that the expression fm(d)P (d, t ) is the probability distribution function of non-blocked pores at time t. It is now possible to calculate the probability that a particle with diameter D goes through the membrane at the moment t. This probability is equal to ratio of the area of non-blocked pores (corrected by the factor i ) having diameters greater than the particle diameter D to the total membrane area. Averaging of this probability over all particles that can go through the membrane pores results in the following expression for the rejection coefcient dependency on time: (t ) = 1 (Nmiyl 2/4S )

If Dmax B dmin (that is, no pore blocking takes place), then and Eq. (7) yields J (t ) = J0. Eq. (7) can be solved in the case of track-etched membranes. In that case all membrane pores have the same diameter dtr and fm(d ) is the Dirac delta function (in this particular case it is reasonable to choose l = dtr). Solution of Eq. (7) in this case results in the following dependency of the permeate volume on time Vtr(t ) = a ln(1 + t Dp ) (8) where Vtr(t ) represent the volume of the solution in the permeate at time t Vtr(t ) = S

&

min(dmax,Dmax)

&

&

Jtr(u ) du ;

dmax

x 2fm(x )P (x, t ) (6)

D min

dx fp(D ) dD

a and are constants, which are obviously independent of time and applied pressure difference: a = J0,trS / Dp,

56

= (J0,tryid 2 trc /4 Dp )

&

V. Staro6 et al. / Separation /Purification Technology 26 (2002) 51 59

Dmax

fp(D ) dD.

In all experiments reported below, the concentration of particles in the feed solution is kept constant; consequently, the concentration dependence is not specied in Eq. (8). Experimental determination of the pure water ux through the track-etched membrane, J0,tr is not difcult; however, it is desirable to determine a and simultaneously in the same experiment. Thus, a and are considered below as tting parameters. Now an important similarity property of MF will be deduced from Eq. (7). For this purpose a dimensionless ux j = J /J0 and a dimensionless time t = t /t * are introduced, where t * = 4/ (iyl 2cJ0). It is necessary to stress that time scale t * is inversely proportional to concentration and pressure difference (because J0 in the denominator is proportional to Dp ). With the help of the dimensionless variables j and t, Eq. (7) can be rewritten as j (t ) = A

Hence, J (t ) can be calculated with the help of J (t* ) shifting the latter dependency along both axes: J (t ) = (Dp /Dp )J [t  Dp c /(c Dp )] (10) Eq. (10) is important with regard to the similarity property of MF processes. An approximate solution of Eq. (7) can be found in the following way. According to a mean value theorem for integrals Eq. (7) can be rewritten as J (t ) = J0 exp (yil 2c / 4)d** 2

&

J (u ) du

dx = J0 exp (yil 2c /4)d** 2

&

&

Dmax

fp(D ) dD A

d**

n & n

dmax

x 4fm(x )

d min

J (u ) du

&

Dmax

fp(D ) dD

d**

&

dmax

d min

exp

 &

x 4fm(x )
t

j (u ) du

&

Dmax

fp(y ) dy dx (9)

Eq. (9) does not include any parameters connected with applied pressure difference or concentration of particles in the feed solution. Therefore, in these special co-ordinates the dimensionless ux j (t ) should be valid for any pressure difference and any concentration. This means, if an experimental curve J (t* ) is generated for xed values of Dp* and c*, and J (t ) is desired for any other values of Dp and c, the following steps are required: according to the denition of the dimensionless time: t  Dp c  = t Dp c,

If we suppose now that d ** value is independent of time the latter equation can be immediately integrated and the solution is as follows k Dp J (t ) = (11) k 1 1 exp( kkc Dp t ) k0 where k = J/Dp is the membrane permeability at the nal stage of the process; k0 = J0/Dp is the initial membrane permeability;

J = J0A

&

dmax

x 4fm(x ) dx ;

D max

k = (yid** 2/4)

&

Dmax

fp(D ) dD

d**

or t = t  Dp c /(c Dp )

according to the denition of the dimensionless ux: j = J /J0 = J /J0, or J = J0(J /J0) = J (Dp /Dp )

Eq. (11) includes three parameters: k, k0 and k. Permeabilities k and k0 can be determined independently and k can be determined by tting only one experimental dependency of ux on time, J* (t ), at a xed pressure difference Dp* and concentration c*. After these three parameters are determined, J (t ) can be easily calculated according to similarity property, Eq. (10), at any pressure difference and concentration. Direct numerical calculations according to Eq. (7) showed that the approximate solution according to Eq. (11) gives in most cases a reasonable approximation of the exact solution of the IDE.

V. Staro6 et al. / Separation /Purification Technology 26 (2002) 51 59

57

Fig. 2. Example of particle size distribution of the water used (dilute colloid solution) for MF experiments on track-etched membranes.

3. Experiments Two series of experiments were conducted. (i) Track-etched membranes were used in the rst series to check Eq. (8); and (ii) a commercially available Teon membrane was used in the second series to verify the similarity property of MF processes according to Eq. (10) and the applicability of the approximate solution according to Eq. (11). Track-etched poly(ethylene terephthalate) membranes (commercial name LAVSAN) were supplied by Dr B. Mtchedlishvily (Track Etched Membranes Laboratory, Moscow Institute of Crystallography, Russian Academy of Sciences, Leninski pr. 59, Moscow 117333, Russian Federation). The experiments were conducted in a standard dead-end MF setup with a membrane area of 32.17 cm2. The cell was pressurised to operating pressure in the rage from 0.2 to 0.9 atm (that is, a typical pressure range for MF) and the permeate volume of water as a function of time was measured. The feed was City of Austin tap water, which served as a dilute colloidal solution. Particle concentration and size distribution in the water were determined using a Coulter Multisizer Counter. A typical particle distribution is shown in Fig. 2. Four track-etched membranes of pore diameters 0.03, 0.1, 0.45, and 2 mm were used. For

each membrane two experimental curves were constructed at different pressures with the same water (dilute colloid solution). Experiments with different membranes were conducted on different days: consequently, particle distribution and their concentration in water might be different for different membranes. As mentioned above, parameters a and were determined using a tting procedure. In Fig. 3 two typical plots out of a series of eight cases are presented in all eight cases (two experiments with each membrane) the theoretical curves according to Eq. (8) are in excellent agreement with the experimental results. According to the theory presented above, parameters a and should be independent of the operating pressure drop (a manifestation of the similarity property in the case of track-etched membranes). To test this, values a and were determined from separate experiments with different applied pressures. As mentioned above, the pressure ranged from 0.2 to 0.9 atm; over this pressure range a and varied by less than 10% in all cases, but in some cases d = 0.l and d = 0.45

Fig. 3. Comparison of experimental dependencies of the water volume in the permeate on time and tted theoretical dependencies (solid lines) in two cases: track-etched membrane with (a) dtr = 2 mm; and (b) dtr = 0.1 mm; (
) experimental points.

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V. Staro6 et al. / Separation /Purification Technology 26 (2002) 51 59

4. Conclusions A theoretical model of the dead-end microltration (MF) process of dilute colloid suspensions is suggested. The model is based on a sieve mechanism and takes into account the probability of the membrane pores blocking in the course of the MF process; an integro-differential equation (IDE) that includes both the membrane pore size and particle size probability distribution functions is deduced. According to the suggested model a similarity property of MF processes is deduced. This property allows one to predict the ux as a function of time for any pressure and concentration (dilute) based on one experiment at a single pressure and concentration. The similarity property is in good agreement with the experimental data on both track-etched and commercial Teon membranes. An approximate equation for ux dependency on time is derived from the IDE and this solution is in good agreement with the experimental results on a commercial MF Teon membrane.

Fig. 4. Experimental and theoretical dependencies of the dimensionless ux on time for the MF Teon membrane MMF: ( ) Dp1 = 0.55 atm; () Dp2 = 1.8 atm; ( + ) Dp3 = 1.05 atm. Solid line corresponds to the tted theoretical dependency j (t1) = j {1 (1 j) exp( k jt1)} 1 with j = 0.03, k = 0.18 min 1.

mm) those variations were less than 1%. The good t of the data and pressure independence of a and support the theory presented here as a description of the MF process for track-etched membranes. The second series of experiments was performed on a commercially available Teon MF membrane having an average pore diameters of 0.35 mm (commercial name MMF, supplied by VNIISS, Vladimir, Russian Federation). Concentration of colloid particles in the feed solution was 55 000 particles per cm3 and the concentration in the permeate was 55 100 particles per cm3; thus, the rejection coefcient was close to 1. In each experiment the initial water permeability, k0, was 0.87 ml cm2 min kPa. In Fig. 4 experimental data for ux versus time for three different pressures are presented. Pressure DP3 = 0.55 atm was chosen as a basis, p . Concentration of colloid particles in the feed solution was xed and according to Eq. (10) experimental curves J1(Dp1t1/Dp3)/J01, and J2(Dp2t2/Dp3)/J02 should lie on the experimental curve J3(t3)/J03. The universal curve (Fig. 4) conrms the similarity property of the MF process. The solid curve in Fig. 4 presents the tted curve according to the approximate solution Eq. (11), rewritten in the following form j (t3) = j {1 (1 j) exp( k jt3)} 1, where k = kcJ03.

Acknowledgements The authors express their gratitude to the Texas Advanced Technology Program and the University of Texas Separations Research Program for their nancial support, to Dr V. Gorsky for his assistance in computer programming and to Mr S. Chakravarti for help in experimental measurements. V. Starov expresses his gratitude to the Royal Society for support (Grant ESEP/JP/JEB/ 11159).

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