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DESALINATION

ELSEVIER
Desalination 143 (2002) 123-139
www.elsevier.com/locate/desal

Modelling of membrane filtration of natural water for potable purposes


Kt-ystyna Konieczny
Institute of Water and Wastewater Engineering, Silesian University of Technology, 44-100 Gliwice, Konarskiego 18, Poland Tel. +48 32 2372020; Fax: +48 32 2372368, e-mail: konkryst@eus.polsl.gliwice.pl Received 13 August 2001; accepted 10 January 2002

Abstract Three different methods have been proposed for the mathematical description of the microfiltration process of natural waters, that is: the model describing the changes of permeate flux in time - the relaxation model, the model of filtration resistance and the Hermia model which allows determination of the mechanism of pore blocking in the membrane. In order to assess the adjustment level of the proposed mathematical models with experimental data, the Fisher s statistical test was applied. The optimal time of filtration and membrane washing cycle for which the yield is the highest was also determined. Keywork Natural waters; Membrane water treatment; Microfiltration; Membrane filtration modelling

1. Introduction

The need to improve existing techniques of water treatment and to introduce new ones results from three basic causes [ 1,2]: (1) gradual deterioration of the quality of water resources, (2) a growing demand for high quality water, and (3) more stringent legal regulations involving the quality of potable water. Different kinds of pollution present in waters used for various purposes - and in the case of surface waters different levels of pollution - result in a situation where their treatment is not easy to
001 l-9164/02/$-

perform, and the treatment system (technological flow diagram) should be worked out individually for each type of water. In order to guarantee the required quality of potable water or water used for industrial purposes, very often unconventional or high-efficiency processes have to be applied (e.g., membrane techniques), which are expected to be safe for the health and lives of the consumers, despite higher costs involved and despite the necessity of introducing procedures ensuring well-organized and professional maintenance of the water treatment system [3].

See front matter 0 2002 Elsevier Science B.V. All rights reserved

PII: SO0 11-9 164(02)00234-5

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K. Konieczny / Desalination 143 (2002) 123%I39

The inconveniences involved in traditional treatment techniques of natural waters require the application of new separation techniques, and membrane methods are considered to be an alternative [4-6]. The main advantages of water filtration using membranes are as follows [7,8]: l invariable quality of produced water l considerably lower amount of chemicals l easy process development (module system) l maintaining the process without interruption under mild environmental conditions l lower consumption of energy as compared with other treatment techniques. The treatment studies carried out [3,1O-l 51on underground and surface waters were highly effective: Both microfiltration and ultrafiltration membranes turned out to be very efficient with respect to disinfection of waters involving coli-type bacteria, whereas mesophilic bacteria were removed in about 92-lOO%, with high yield depending on the compactness of the membrane. The obtained coli index in the treated water was always lower than that required by the Ministry of Health and Social Care [16], and WHO and EC regulations. Apart from bacteria, turbidity was also totally eliminated in the membrane treatment of water. Iron and manganese compounds were removed in 50-l OO%, and the level of organic compounds removal depended on the character of the substance and type of membrane. The remaining parameters ofwater quality did not practically undergo any changes, or they changed to a considerably lower degree. The content of each of the investigated factors in permeate is within the standards for potable water. Based on the hydrobiological analysis, we can say that ceramic membranes retain water organisms at the level close to 100%. The membranes and membrane modules applied in the treatment process of water should

Without backflushing Time

Fig. 1. Cyclic changes of permeate flux in time (process of the filtration and regeneration of membranes).

allow easy regeneration (cleaning) using backflushing and should have high compactness (packing density) [2,5,17]. During the membrane process, a high drop of permeate flux (filtrate) is initially observed, which gets stabilized at a constant level after some time (Fig. 1). The stabilization of permeate flux for polymeric and ceramic membranes takes place within 60-122 min whereas for capillary membranes it amounts to 100-3 84 min [3]. It follows from the investigating studies carried out so far that the process is run within the range of stabilizing permeate flux, which does not ensure optimal yield. The thesis of the work is based on the assumption that, in order to obtain such an optimal yield, the membrane process should be carried out in unsteady conditions (in the area where the permeate flux is going down). Irreversible fouling of the membrane pores is created within a short time and at the initial stage of filtration cycle, and then is stabilized over a long period. That is why the principal change of yield is connected with reversible membrane fouling. The stabilization of the flux takes place at a considerably lower level than the initial one. In order to obtain the optimal efficiency, the

K. Konieczny / Desalination 143 (2002) 123-139

125

process should be stopped at the right moment and the regeneration of the membrane should be carried out (Fig. 1) to remove the reversible fouling particles and to restore a high yield close to the initial one. In order to prove that the following procedures had to be effected: define the flux of one cycle of membrane processes in the treatment of water for municipal purposes-the next cycle will take place with the same character but with lower value; find the mathematical description of the process; get acquainted with the mechanisms accompanying the membrane processes; define optimal operating conditions for membrane modules (max. yield).

of surface waters.

Fig. 2. Diagramof the apparatusfor membranefiltration M, manometers; V, valves.

2. Experimental 2.1. Apparatus and membranes Fig. 2 presents the apparatus used for the membrane filtration of raw water. The basic elements of the installation for membrane filtration of water were as follows: a 19-channel module with a ceramic membrane (Micro Kerasep) with an area of 0.06 m2, impeller pump (Grundfos), water tank and necessary instrumentation: valves, manometers, thermometer and telerotameter. The following ceramic membranes of from Tech-Sep were applied in the testing: microfiltration membrane KOOW4040 (pore diameter 0.1 urn) microfiltration membrane KOOW5040 (pore diameter 0.2 pm) microfiltration membrane KOOW6040 (pore diameter 0.45 pm). The characteristic of the applied membranes was as follows: l ceramic support, composition of the active layer of the membrane TiO, or ZrO,

Support diameter 20 mm, length 400 mm, channel diameter 2.5 mm, 19 channels Resistance to pressure 5.0 MPa, working pressure 1.2 MPa, Resistance to pH within the range O-14, resistance to temperature max 673 K Resistance to solvents. For the purposes of the testing, surface water was came from the intake at Strumien (south part of Poland) situated at the Vistula River. The actual testing was carried out in the closed cycle within the period III-V 99. The temperature of raw water was oscillated within 279 to 285 K. 2.2. Methodology The membranes were conditioned by passing deionized water through the system over 16 h in order to obtain stable operating parameters. The conditioning of membranes was carried out in the closed cycle, i.e., the permeate was returned to the feed tank. The conditioning parameters were as follows: pressure 0.1 MPa, temperature 297 K and cross-flow velocity 4 m/s. Then the membranes were tested with deionized water to determine the changes of volumetric permeate flux over 5 h under a pressure of 0.1 MPa for particular membrane time; additionally for membrane 0.2 urn, the testing was carried out at pressures of 0.15 and 0.2 MPa. The investigations with natural water were carried out using an open system (Fig. 2). The feed was collected directly from the raw water reservoir, and the permeate and retentate were

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143 (2002) 123-139

returned to the tank. The testing cycle lasted 10 h. The filtration was carried out under invariable operating conditions: pressure 0.1 MPa and cross-flow velocity 4 m/s. The temperature of raw water was oscillated within 279 to 285 K. The final testing of the membrane with deionized water was carried out in the same way as the preliminary one. The main objective was to determine wear and tear of the membranes (changes in capacity) and the need to carry out a regeneration process of the membranes. Comparison of deionized water fluxes before and after filtration of natural water made it possible to determine reversible and irreversible membrane fouling.

3. Results and discussion


3. I. Experimental water JIux change

In order to confirm the work thesis involving the need to apply membrane filtration processes within changeable, unstable permeate flux, and in order to verify mathematical models describing the membrane process, as well as to assess correlation quality of these models with experimental data, dependencies of volumetric permeate flux over time were determined (Fig. 3.) The following was determined for each membrane: dependence of the volumetric flux of deionized water (4,) on time for a new membrane - not previously used dependence of the volumetric flux of natural water (J,) on time dependence of the volumetric flux of deionized water (J,) on time, after 40-60 h of membrane operation. The analysis of results of such a sequence of investigation studies made it possible to define the share of particular components of process resistance being the consequence of different types of membrane pores blocking (reversible and irreversible fouling).

Analyzing the results obtained for the 19channel ceramic membranes, it was found that the volumetric flux of water decreases over time. The value of volumetric permeate flux during the microfiltration of surface water is respectively lower than the values for deionized water. The results of measurements evaluating the drop of volumetric permeate flux caused by fouling of membranes are reflected by the curve presented in Fig. 3, final test-deionized water. We can observe the increase in the efficiency of permeate flux with the increase of measurement pressure (Fig. 3a,d,e). Similar values of volumetric permeate flux for membranes of the porosity 0.1 urn and 0.45 urn (according to manufacturer s data) can be explained by various packing densities of pores in these membranes. The membrane of 0.2 urn porosity is characterized by twice as high volumetric flux, which was a decisive factor in selecting this membrane to carry out studies on natural waters using diversified pressure.

3.2. Modelling of membrane filtration process The modeling of the membrane filtration process of natural waters was based on the following: on membrane filtration in non-stationary process and on a mathematical model explicitly describing the changes of permeate flux in time on the mathematical model describing the changes of mass transport resistance during the membrane filtration in time on the Hermia model [ 181 involving the filtration under constant pressure conditions, which allows defining the most probable mechanism of membrane pore blocking. Also, the assessment of correlation quality level was carried out involving the models with which the change of permeate flux in time can be described in view of the experimental data obtained from water testing, and the method for

K. Konieczny / Desalination 143 (2002) 123-139


4

127
I

i . .

a)

new membrane-deionized water 1 mnatural water A final test-deionized water

b)

new membrane-deionized water n natural water A final test-deionized water


l

1 ,

__I_ 0

.
100

200 t [min]

300

100 t [min]

200

300

new membrane-deionized water m natural water A final test-deionized water

..,..

7;

.,...

m ,...,,

,...

,..... .,... .,
0 0

,.....-._

^..

..,__l.l.. , ._._,.._.. ,,,_ ,_._ .. .. _.!_ ,,._.., -. ll- l_ ,.,_I_., .., 100

200 t [min]

300

100 t [min]

200

300

new membrane-deionized

water j

Fig. 3. Dependence of volumetric water and permeate flux passing throughthelPchanne1 ceramic membranes over time for surface water from Strumien:(a) membrane 0.1 pm (0.1 MPa), (b) membrane 0.45 pm (0.1 MPa), (c) membrane 0.2 pm (0.1 MPa), (d) membrane 0.2 pm (0.15 MPa), (e) membrane 0.2 vrn (0.2 MPa).

calculating the optimal time to be used for the process of membrane filtration was presented. 3.2.1. Membrane filtration model in nonstationary process (relaxation model)
..,
0 100

200 t [min]

300

The changes of volumetric permeate flux (J) in time (t) can be described using a kinetic equation in which the decrease of permeate flux

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K. Konieczny / Desalination 143 (2002) 123-139

is proportional to its value:

The equation is true if we allow for the condition J(0lPo = Jo* The solution of the above equation leads to the following relation: J-J, -=e 2 (2)

Jo-J*

Eq. (2) was used to determine the time constant t,,, which characterizes the decline rate of permeate flux:
to

the curve illustrates the correlation of the function described by the equation. In the initial stage of the membrane filtration (Figs. 3 and 5), the processes that take place are more complex than would be expected from the model presented. Yet, the further run of both the experiments and the results from the model indicate that their correlation is very good. Making use of Eq. (4), we can predict the change of permeate flux during the operation of membrane systems knowing only three quantities which characterize the filtration process described by the model (1): JO - initial permeate flux, J, -equilibrium permeate flux and time constant - t,,, and the determined constants can be used for the optimization of the complete cycle of filtration process, i.e., for the determination of optimal time (to,,). 3.2.2. Hydraulic model ofBltration resistance

II
a

(3)

Fig .4 presents the determination and then calculation of the value to from the above equation for the filtration of water and all ceramic membranes. After the transformation of Eq. (2) we obtain a formula which can be used to calculate the dependence of the (instantaneous) theoretical volumetric flux on time:

The modeling of the filtration yield can be also based on the analysis of resistances [3,19,20] encountered by the liquid passing through the membrane, and by allowing for the phenomena affected by mutual the interaction of membrane and substances present in natural waters. In order to determine particular components of the resistance, we used the dependence of volumetric permeate flux (J,) on transmembrane pressure (AP), allowing for hydraulic resistance encountered by the liquid flowing through the membrane:
J,= dp '1'40tal

J,(t) = &,-J_)e - +J,

(4) (5)

By calculating the theoretical (instantaneous) volumetric flux of the permeate over time, we could compare these values with true values of volumetric permeate flux obtained during the studies of natural waters. Fig. 5 presents exemplary results from the investigation studies obtained from the water treatment plant at Strumien. The points on the picture illustrate the results of experimental measurements, whereas

The total hydraulic, resistance is the sum of component resistances, e.g., of the membrane resistance R,,,and the sum of resistances resulting from concentration polarization and fouling. The resistance connected with concentration polarization can be disregarded since the concentrations of pollution present in water are too low to effect the formation of a polarization layer which

K. Konieczny / Desalination 143 (2002) 123-139


t

129 [mini 500


t

[min] 0 100 200 300 400

50

100

150

,-.-1
!

-1

3
~o -2 ~3

--= -3
"S -4
..................................................................................................................................................................................... i

_=
-4

............................................................................................................................... i--*i
.................................................................. ....................................... 2. ...........

-5

50

100

150

200

t [min] 250

50

100

150

200

t [rain] 250

.........

~-2 _=

_=
-4 ........................................................... ............................................................ [ ~................................ 4

-3

-5 ................................... :.................................... : ............................................................................................................

Fig. 4. Method of determination of characteristic decline time (to) of membrane filtration for surface water from Strumien treatment plant: (a) membrane 0.1 ~tm (0.1 MPa), (b) membrane 0.2 ~tm (0.1 MPa), (c) membrane 0.2 Itm (0.2 MPa), (d) membrane 0.45 ~tm (0.1 MPa).

could have any substantial influence on the total resistance. The resistance connected with fouling has two components: the resistance connected with reversible fouling (Rfo) and the resistance connected with irreversible fouling (Rf,). Hence, Eq. (5) can be presented in the following form: AP 11 "~m

The following must be done to determine particular components o f the resistance: determine the relations J,v = f i t ) for a new (clean) m e m b r a n e and for deionized water, whereby we can calculate the m e m b r a n e ' s resistance R=, calculate the total resistance Rtot~ from a similar relation obtained for natural waters: AP
Rtotal -

+ rfo + Rfn)

(6)

11"Jr

(7)

K. Konieczny /Desalination

143 (2002) 123-l 39

+ J experimental flux

-J

J experimental flux theoretical flux

50

100

150

200

250

100

200

300 t [min]

400

500

600

t [min]

/
+ J experimental flux -J theoretical flux

d)

J experimental flux theoretical flux

-J

I
0

I
100 t [min] 200 300
0

50

100

150 t [min]

200

250

300

Fig. 5. Dependence of experimental and theoretical volumetric flux (relaxation model) over time for 19-channel ceramic membranes and water from Strumien treatment plant: (a) membrane 0.1 pm (0. lMPa), (b) membrane 0.2 pm (0.1 MPa), (c) membrane 0.2 pm (0.2 MPa), (d) membrane 0.45 pm (0.1 MPa).

define the dependence of volumetric flux of deionized water in time for the membrane after the testing on natural waters, whereby we can calculate the sum of resistances R,,,+ R, l calculate the resistance of reversible fouling (&,) and irreversible fouling (R,) from the difference of resistance value obtained from the three measurement series mentioned above. Fig. 6 presents the dependence of resistance change during the filtration of surface water from the Strumien water treatment plant over time for the ceramic membranes. It follows from the
l

obtained results involving the dependence of hydraulic resistances over time that the irreversible resistance is formed in the initial, short time of the process and the yield depends on the reversible resistance changeable in time. In order to define the changes of reversible resistance, we assumed that this resistance is proportional to the amount of substance deposited on the membrane, which is expressed by the following equation:

$(R_-R)+J--(R_-R)=O

C-9

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131

versible resistance I Rfo, reversible resistance I Rm, membrane resistance x Rtotal total resistance

100 t [min]

200

300

100

200 t [min]

300

,
l n

Rh, inreversible resistance Rfo, reversible resistance

A Rm membrane resistance

-I--. -... . .. .

..- ~. . .

..- ..-_...... _.

100

200 t [min]

300

100 t [min]

200

300

Fig. 6. Dependence of resistance change &, R,,, R,, Rfi over time for ceramicmembranes (19-channel) during filtration of surface water from the Strumien treatment plant: (a) membrane 0.2 pm (O.lMPa), (b) membrane 0.2 pm (0.15 MPa), (c) membrane 0.2 pm (0.2 MPa), (d) membrane 0.45 pm (0.1 MPa).

By integrating Eq. (8) and allowing for the fact that R,= 0 in t = 0, we obtain the following: [ [_;]I R, = Rm 1-exp

(10)

Eq. (9) contains two constants - R, and tm which can be determined based on experimental data. Transforming Eq. (9) to the form:

and by finding the logarithm, we obtained equation of the straight line running through beginning of the coordinate system. From inclination of this line we determined coefficient tRo(Fig.7). In order to verify the proposed model,

the the the the we

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K. Konieczny / Desalination 143 (2002) 123-I 39

t [min] 0 50 100
150 200 250 0

t [min] 0
50 100 150 200

-1 $ 2 -2 -3

.__

b)

CJ -4 4 -5 -6

I
0 50 100

..
l

t [min] 0
50

t [min]
150 200 250

100

150

200

250

. .__._._ _._..___._ ._._ __^ ___^._ .__ ^...^ _______ .._^ _.._...-.._ -6

Fig. 7. Dependencedescribed by Eq. (10) for surface water from the Strumien treatment plant: (a) membrane 0.2 pm
(0.1 MPa), (b) membrane 0.2 pm (0.15 MPa), (c) membrane 0.2 pm (0.2 MPa), (d) membrane 0.45 pm (0.1 MPa).

calculated the values of resistance formed in effect of the occurrence of reversible fouling, using Eq. (9). Then, the volumetric permeate flux described by Eq. (6) was calculated by inserting the values of membrane resistance and the resistance of irreversible fouling determined from the experiment, and the value of reversible resistance calculated from model Eq. (9). The dependencies obtained from model calculations as well as the measurement points are presented in Fig. 8. They confirm good correlation of the proposed model with the obtained experimental results. It is further confirmed by the high

correlation coefficients (see Table 3). Table 1 presents the calculated values of constants in Eq. (9): coefficient fR,, and the resistance connected with reversible fouling after an infinitely long time period. The resistance model connected with reversible fouling is true, but it requires a larger number of experiments to be carried out. It is necessary to characterize the membrane using deionized water with both the new membrane and the one after the operation in order to determine particular components of resistance occurring in Eq. (6).

K. Konieczny / Desalination 143 (2002) 123-I 39

133

100 t [min]

200

300

t [min]

100

200

300

100

200

300

t [min]

t [:min]

Fig. 8. Dependence of experimental and theoretical volumetric flux (calculated with reversible resistance model) over time for investigated membranes-(a) membranes 0.1 urn (0.1 MPa), (b) membranes 0.2 urn (0.1 MPa), (c) membranes 0.2 urn (0.15 MPa), (d) membranes 0.2 urn (0.2MPa) - and waters from the Strumien treatment plant.

Table 1 Values oft,, obtained from the calculations for the investigated membranes and waters No. of measurement series Membrane type, MF Resistance, R, * 10-12, m- Value tR,, calculated from Eq. (lo), min-

Size, urn 1 2 3 4 5 0.1 0.2 0.2 0.2 0.45

MPa 0.1 0.1 0.15 0.2 0.1 2.314 3.474 2.372 3.348 0.478 60 94 55 81 370

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K. KoniecznylDesalinationI43 (2002)123-139

3.2.3. Mechanism of pores blocking during membrane f&ration in constant pressure conditions (Hermia model) The present model describes the change of process yield using a two-parameter equation [18]: Fig. 9. Mechanism of membrane pore blocking.

(11)
It can be applied as a criterion to identify various mechanisms of pores blocking in the membrane (Fig. 9). Assuming that parameter n can have four discrete values [n = 2 (complete membrane blocking), n = 3/2 (standard blocking of pores inside the pores), n= 1 transitory blocking of pores and n=O (cake blocking of pores)], the second constant k in each case has a different dimension, which is a bit troublesome while analyzing the process. A verification of the Hermia model was suggested for the description of the pore-blocking mechanism in the treatment process of natural waters. For this reason, Eq. (11) was complemented with the following boundary conditions:

l t, t

Fig. 10. Graphic interpretation of dimensionless

fluxj,.

After the transformation,

(1%
Eqs. (11) and (15) explicitly contain two parameters k and n or (k, and n). By respective transformation of conditions (12) for Eq. (15) we obtain:

V(t)
or

t=O

and

dV =F/J, dt t=O

(12)

Vt>l
tcO

anti VOl

r_to

V,

(13)

Wl,=O= 0 and
and
i,=J;

r=O=jo; u(~),,~ = 1
J=

u(r),,o=

0 (16)

In order to determine a dimensionless value of the coefficient k, dimensionless quantities of volume (u) and time (7) were introduced:

Js

l. .
A,
to

(14)

Based on the obtained measurement results,

K. Konieczny / Desalination 143 (2002) 123-l 39

135

that is permeate volume in a time unit from a given area of the applied membrane, we obtain the following dependence:

~(t>l~=~ =0

and

u(T)[,,~ =1

(19)

Therefore,

t=o

(17)

A basic experimental parameter which allows interpreting the Hermia model is the dimensionless initial fluxj, from which we can draw conclusions as to the mechanism of pore blocking in the membrane. Graphical interpretation for the determination of parameter j, is presented in Fig. 10. As can be seen from Fig. 10, a precise determination of the parameter j, necessitates a precise determination of characteristic time to,the obtained value of volume V, corresponding with time to as well as a precise determination and analysis of the initial yield of volumetric permeate flux over the first few minutes of the filtration process. As follows from the definition described by Eq. (17), parameterj, is expressed as the ratio of the tangents of the inclination angle of the tangent to the secant, and it can be described by the following equation:
j. = -

Qcl >1

and solving Eq. (15), the conditions (16) and (19) being satisfied, we determine constant k which describes the mechanism of the process respectively for the values n = 0, 1, 3/2 and 2. The solution of Eq. (15) assumes an explicit form by which we can interpret the mechanisms of membrane blocking as well as carry out a comparative analysis of the experimental curve and model curves for particular values of exponent n. The calculated correlation coefficient is the measure of the correlation of the curves. The highest value of the coefficient stands for the best correlation between the model and the experiment (Table 2). Based on the values of correlation coefficients (Table 2), we can observe that the mechanism of pore blocking consists in cake blocking of pores (n=O), which is connected with the formation of a layer of substances retained on the membrane s surface. This phenomenon lowers the yield of the membrane filtration process. The values of correlation coefficients indicate that the way in which the pores of the investigated membranes are blocked cannot be unequivocally defined since the values of correlation coefficients for particular values of n are not much different from each other. Therefore, it is safer to say that during the membrane filtration process a mixed blocking mechanism ofthe membrane pores takes place with the predominance ofthe cake blocking mechanism. This means that the majority of particles present in water affect the formation of a thin layer on the membrane s surface through the accumulation of the substances retained during the filtration process. 3.2.4. Quality Jiltration models
assessment of

UP

(18)
membrane

Using the experimentally determined parameter j,, we can solve the Hermia equation (15). The conditions expressed by Eq. (13) assume the following form:

In order to assess the correlation quality of the proposed membrane filtration models, the Fisher s test was applied [2 11,which can help us

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K. Konieczny / Desalination 143 (2002) 123-139

Table 2 Values of the correlation coefficient for different values of n and for surface water microfiltration membranes obtained from the Hermia model MF membranes Correlation coefficient, r n=O n=l n = 312 n=2

using ceramic

Value of correlation coefficient max., r 0.8845 0.9937 0.9627 0.9592 0.7785

0.1 pm, 0.1 MPa 0.2 pm, 0.1 MPa 0.2 pm, 0.15 MPa 0.2 pm, 0.2 MPa 0.45 pm, 0.1 MPa

0.8845 0.9937 0.9627 0.9592 0.7785

0.8776 0.9901 0.9615 0.9527 0.7695

0.8743 0.9878 0.9606 0.9489 0.7655

0.8712 0.9849 0.9595 0.9449 0.7622

Table 3 Correlation coefficients obtained level from the Fisher s test No. of experiment series V,, dm to, min

forthe appliedmodels in view of experimental data as well as the values of significance

Correlation coefficient

Fisher s test values

Relaxation model 1 2 3 4 5 3.26 7.00 13.0 12.5 4.19 60 78 96 88 60 0.8625 0.9679 0.9601 0.9290 0.9201

Resistance model 0.8744 0.9919 0.9541 0.9619 0.8055

Hermia model 0.8845 0.9937 0.9627 0.9592 0.7785

Frelax

F,ismce

FH~~A

17.43 88.98 70.72 37.81 33.11

19.48 365.88 60.89 74.27 11.08

21.6 471.7 75.96 69.06 9.23

to evaluate whether the variance eliminated by the model is significant comparing with the remaining variance estimated on the experimental basis. The value of Fisher s test was calculated according to the equation

that for the investigated series of membrane filtration of natural waters, in two cases the highest probability for the presented hypothesis (series 1,3) indicates that the models studied are equivalent, whereas with respect to three cases (series 2,4 and 5) the equivalence of the models is of double character. 3.2.5. Determination of optimal operating conditions for membrane modules In practice, the process of membrane filtration should be carried out in the way which would ensure maximum amount of permeate (yield, Q) per one cycle of time, i.e., summary filtration

Correlation coeffkients for the proposed models and the calculated values of significance level for particular models are presented in Table 3. The application of the Fisher s test for the variance having the significance level 0.05 shows

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137

and

,<

JV(r+r)-jJV.d =

(24)

exp -4to k+rp+rO)= to-$.$ 0 ( I

(25) -

25

50 t [min]

15

100

Fig. 11. Dependence ofthe changes of process yield Q on time (Eq. 21) for surface water at the Strumien water treatment plant, using 19-channel ceramicmembranes.

Having Eq. (25), we can calculate the optimal process time t (t,,,,) using the numerical solution method due to t. In order to do so, the trial-anderror method (interpretation one) was applied, which consists in transforming Eq. (25) to Eq. (26) and then comparing the obtained value to the preset one.

time and washing time:

Q=--

J/dt

(21)
t n=o
= to

t +$

The function Q has its maximum, which is illustrated in Fig. Il. For optimization calculations we used the dependence of volumetric permeate flux on time resulting from the relaxation model:
J,, = (Jo-J_)exp (

-t
I

+J,

(22)

As can be seen from Fig. 11, function Q initially rises very fast, reaching its maximum, and then steadily decreasing. To find the optimal point, the first derivative must be calculated and compared to zero. By the differentiation and transformation of Eqs. (21) and (22), we obtain:
I

(23)

Then the preset value is corrected and again the next approximations of optimal process time are calculated. The procedure should be repeated until the satisfactory correlation is achieved (e.g., 3-4 times). By following the above steps, we can define the optimal time for membrane filtration of waters. The dependence presented in Fig. 11 is characterized by a fast increase of the maximum value, and then a steady drop of Q is observed. From the practical point of view, it is more beneficial to realize the process for slightly longer filtration times than topt (by about 20%) since a potential reduction of yield per one cycle is insignificant. The realization ofthe process for times shorter than the optimal one results in a sharp drop of the yield. Optimal realization times of the filtration process for selected cases are presented in Table 4.

138

K. Konieczny / Desalination I43 (2002) 123-l 39

Table 4 Calculated values of optimal times for selected cases Membrane type (MF)/ no. of measurement series 0.1 pm, 0.1 MPa/l 0.2 pm, 0.1 MPa/2 0.2 pm, 0.15 MPa/3 0.2 pm, 0.2 MPaf4 0.45 pm, 0.1 MPa/S Value topt[calculated from Eq. (26), min] 38 31 43 39 36

JO
J,

Value of Fisher s test Volumetric permeate flux, m3xm-* x s-1 Initial volumetric permeate flux J(t)lp4 = Jo, m3xm-*xs- Saturation (equilibrium) volumetric permeate flux, J(t)l,_- = Jm, m3x
m-*x s-l

Js JV JW
Jo m

Average volumetric permeate flux with respect to initial area, m3x


m-*xs-

4. Conclusions So far the selected models have not been used for the description of membrane filtration processes of natural waters. The analyzed models relaxation, resistance, and Hermia - provide a perspective for the assessment of the nature of analyzed phenomena, but none of them provides a universal description of the process for all waters and module (membrane) types studied. The Fisher s statistical test to assess the correlation level of the proposed models with experimental data confirms accuracy of the selection of the models. The obtained dependence of permeate flux change on time was furthermore subjected to mathematical analysis in order to define optimal duration time of filtration and washing cycles of membranes for which the efficiency is the highest. The search for the optimal solution, the acquisition of maximum unitary volume of permeates within one-cycle, resolves itself into a simple optimization task with a single objective functions

AP
P

Q
R Rtotal 2

% r t tP topt
to
t RO

5. Symbols A A,
a

Membrane area, m* Initial filtration area, m2 Inclination of a straight line, s-

Kl n, k

Natural water flux, m3xm-*xs- Deionized water flux, m3xm-*xs- Dimensionless initial volumetric permeate flux Number of parameters in the model Transmembrane pressure, Pa Number of measurements used for calculation of correlation coefficient Maximum yield of permeate per one cycle of time, m3xm-2xs-1 Hydraulic resistance, m- Total hydraulic resistance, m-r Membrane resistance, m-l Resistance of irreversible fouling, m- Resistance of reversible fouling, m- Resistance of reversible fouling after infinitely long time period, m-r Correlation coefficient Time of the filtration process, s, min Membrane washing time (regeneration time tp = 180 s), s, min Optimal time of the filtration process, s, min Time constant in Eq. (l), s, min Constant determined from Eq. (8), s, min Volumetric efficiency of filtration after time t, m3 Volume of filtrate after time to, m3 Constants characterising the mechanisms of filtration process

K. Konieczny / Desalination 143 (2002) 123-I 39

139

Greek

rl
T

Dynamic viscosity of liquid, Pa-s Dimensionless time Dimensionless volume

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