Part A, section 2

Enhancement of critical flux of particulates~

implications for RO desalting processes
A.G.Fane,
UNESCO Centre for Membrane Science and Technology,
University of New South Wales, Australia 2052

1. The concept of critical flux

The concept of critical flux is that for a given feed species and hydrodynamic
environment there is a flux below which fouling is negligible. For particulate solids,
including turbidity and bacteria, the critical flux concept implies that the convective
forces due to flux are balanced by the back transport forces. Once flux is incremented
above critical flux the particles start to deposit forming a cake layer on the membrane.

The well-known film model is based on a balance of convection and back diffusion, and
is given by,

J = k ln (CW C B ) (1)
For small colloids, say < 0.1 µm, the mass transfer coefficient k is given by (D/δ), where
D is the Brownian diffusion coefficient and δ is the liquid boundary layer thickness. The
boundary layer thickness decreases with increase in crossflow velocity, ie the mass
transfer coefficient improves. It should be noted that equation (1) applies to an individual
species , including solutes and colloids, and the value of k will vary with D for each
species. For particles typically > 0.5 µm the Brownian diffusion coefficient is very small
because D α 1/(particle size,ap), but other mechanisms which are driven by the
hydrodynamics and velocity gradients apply. It is commonly accepted that Shear-Induced
diffusion, Ds, becomes important, so equation (1) becomes,

J = k S ln(CW C B ) (2)

where kS = (DS/δ) . Importantly DS increases with particle size (ap) and this leads to
equation,

(
J = 0.078γ a 4p L )
1/ 3
ln(CW C B ) (3) ref [1]

Here γ is the shear rate ( a function of crossflow velocity). This shows that flux J
increases approximately with (particle size)4/3. It should be noted that as particle size
moves from very small to micron size the backtransport mechanism moves from
Brownian to Shear-Induced diffusion and this leads to a minumum in backtransport for
particles in the 0.1 to 0.2 µm range. We have shown [2] that equation (3) describes the
critical flux of several supramicron particles tested with the coefficient 0.078 replaced by
0.06, ( i.e. equation (3) overestimates by about 25%). Figure 1 shows our data which

1
were obtained with the Direct Observation Through the Membrane (DOTM) technique
[2]. With DOTM we can adjust flux to identify the critical flux for the given particle and
hydrodynamic regime.

1000

Latex 11.9
800
SID-MOD, 11.9
Critical flux (l/m h)
2

Latex, 6.4
600
SID-MOD, 6.4

400 Yeast, 5

SID-MOD, 5
200
D = 0.1 φ w a2γ 0
0
0 0.2 0.4 0.6 0.8 1
Crossflow velocity (m/s)

Figure 1. Critical fluxes of latex particles by DOTM [2]

If we could apply an additional backtransport mechanism it would be possible to increase

critical flux. Assuming the additional mechanism is vectorially additive the critical flux
equation for large colloids and micron sized particles becomes,

J CRIT = k S ln(CW C B ) + VE (4)

where VE is the enhancement velocity.

1.1 Enhancing critical flux

If critical flux of particulate foulants could be increased this would either eliminate or
reduce the rate of fouling deposition. The AC field effect ( see Coster Report [3]) could
have two potentially enhancing effects.
(i) Particle Aggregation.
The critical flux depends on particle size (see equation(3)) and larger particles have larger
shear-induced diffusion coefficients. Typically as size is doubled the critical flux is
doubled. The dipole-dipole interactions induced by non-uniform AC field gradients can
lead to aggregation of particles [3], and this should increase JCRIT.
(ii) Enhanced Transport
The dielectrophoretic force induced by the non-uniform AC field could also result in a
velocity vector normal to the membrane surface.. As seen in equation (4) this vector,VE,
could be additive in its effect. It should be noted that depending on the field gradient and
particle properties the field effect could enhance or diminish critical flux; the net effect
depends on the sign of the field effect velocity vector. The Coster report [3] emphasizes
the importance of the AC field frequency in determining the magnitude of the field effect.

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2. Critical Flux in Spiral Wound Modules (SWM)

The SWM has net-like spacers in the thin flow channels. These spacers create eddies and
increase surface shear and thereby decrease the boundary layer thickness. Typically the
conventional mass transfer coefficient , k in equation (1), can be increased by an order of
magnitude by using spacers (the penalty is a 100 fold increase in channel delta P pressure
losses) . We have examined the effect of various spacers on critical flux of particles using
a test cell and the DOTM system to determine critical flux. Figure 2 shows JCRIT data for
a 6 µm model particle and various spacers. It is evident that spacers can increase critical
flux by up to 2 to 3x compared with an empty channel.

300.0

250.0

200.0 Spacers
Critical Flux (LMH)

150.0

100.0

50.0
No Spacer
0.0
Jcrit α (dp)4/3

-50.0
0 100 200 300 400 500 600 700 800 900 1000
Reynolds Number
Slit Channel 0.028"/90° 0.028"/45° 0.028"/0°
Slit Channel LR 0.028"/90° LR 0.028"/45° LR 0.028"/0° LR

Figure 2. Critical fluxes of latex with and without spacers by DOTM [4]

The critical fluxes in Figure 2 are in the range 100 to 200 l/m2h which are much greater
than in a typical SWM. However particles of interest are submicron size. If the measured
JCRIT values are adjusted according to ( size)4/3, ie based on equation (3) the fluxes in
Table 1 are estimated,

Particle size ( microns) Estimated Jcrit (lmh) Estimated Jcrit (gfd)

1.0 9-18 5-11
0.5 4-8 2-5
0.2 1-2 0.6-1.2

Table 1 Estimated critical fluxes of submicron particles in SWM (basis Fig 2 and equ.(3))

The estimated critical fluxes in Table 1 are lower than many SWM applications. In other
words these particles would tend to deposit for conditions where the local flux exceeds
the local JCRIT.

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3. Particulate Fouling SWMs

The rate of deposit (mass/time.area) of particulate foulants on a membrane can be

represented by [5],

dm dt = C B ( J − J CRIT ) (5)

In other words the rate of deposition depends on the foulant content (CB) and the net
convection given by (J-JCRIT). Thus the lower the imposed flux , or the higher the critical
flux, the slower the rate of deposition. In principle if JCRIT < J the rate becomes negative
and particles are removed. In practice this depends on the reversibility of the deposit.

3.1 Foulant resistance

The mass load (m, kg/m2) of particle foulant will produce a fouling resistance, RF, which
can be expressed by,

RF = mα C (6)

where αC is the specific cake resistance (m/kg) and from filtration theory αC is a strong
function of the particle size . From the Kozeny-Carman relationship,

α C = 180(1 − ε ) /( ρ P d P2 ε 3 ) (7)

Thus the smaller the particle the greater the fouling resistance for a given load of foulant;
in fact a 0.1 µm particle would have about 100x the specific resistance of a 1 µm particle
(due to the dependence on size-2 in equation (7)). Equation (6) can be rewritten in terms
of the cake height, δC, as,

RF = (δ C (1 − ε )ρ P )α C (8)

We can use this to examine the effect of a model particle (silica colloid, density 2200
kg/m3) on permeability. Table 2 shows estimated changes to permeability when using a
typical RO membrane ( Rm=1x1014m-1) due to a thin cake layer of different size particles
(assumes 12.5 µm thickness and voidage of 0.3).

Particle Size (nm) Permeability* (% initial)

20 50
100 96
500 99.8

Table 2. Estimated permeability due to thin deposit layer of particles

[* (Rm/(Rm+RC))x100]

4
An obvious conclusion from Table 2 is that only very small colloids are likely to have a
significant effect. This points to an obvious benefit of increasing particle size by
aggregation. However, this is a very idealized ‘cake’ and for more practical contaminants
there are likely to be other components, such as NOM and macromolecules. If these
components ‘fill the voids’ of larger particle cakes the permeability loss could be
significant. A similar point can be made about biofilms and bacterial layers where
components such as EPS are present.

3.2 Cake Enhanced Osmotic Effect

The cake enhanced osmotic pressure effect (CEOP) was identified by Hoek and
Elimelech.[6]. CEOP effect occurs due to an increase in concentration polarization (CP),

CP = CW / C B (9)
From equation (1) we see that ,

CP = exp( J / k ) . (10)
In a typical RO plant CP would be < 1.2 , and this is achieved by selection of flux and
system hydrodynamics (which determines k). CP is important because it influences solute
transmission and because if determines the osmotic pressure at the membrane surface.
Flux relates to driving force and resistance by,

J=
(∆P − CP∆π ) (11)
µ (Rm + RC )

where ∆π is the osmotic pressure difference between the feed (at CB) and the permeate
stream. Equation 10 shows that performance will drop if RC --> Rm, and if CP becomes
significant. Figure 3 depicts the difference between a clean membrane and one with a

C w*
Bulk Bulk
Cw
Flow Flow
Membrane

Membrane

Cb Cb
Fouling

C p*
Cp

Cw − Cp *
C w * − C p*
CP = CP =
Cb − Cp C b − C p*
(a) Before membrane is fouled (b) After membrane is fouled

5
 Figure 3: Concentration polarization in a reverse osmosis membrane system

cake layer of particulates. The surface concentration of salt increases from CW to CW*
due to the cake layer. The CP is increased by the unstirred layer of liquid present in the
cake which is not thinned by the crossflow in the feed channel so the ‘boundary layer’
thickness , δ, is now the cake layer thickness, δC. In addition the diffusion coefficient of
the salt ,D, is less in the cake than in the free solution, ie

DCake = Dε / τ (12)

For example for a cake with voidage 0.3 and tortuosity (τ) of 3.0 the cake diffusion is
only 10% of that in the free solution.

The significance of this can be illustrated by estimating how a CP of 1.2 would change if
the diffusion in the polarized layer dropped to 0.12. Assuming the cake layer height δC is
similar to the boundary layer height without fouling ( it could be more, or less ), then
with a mass transfer coefficient kCake equal to 0.1k, and applying equation (10) the CP
would rise to 6.2. This would have a major effect on ∆π and the apparent permeability of
the RO membrane.

Figure 4 (from [7]) shows changes due to fouling resistance RF and CP for a membrane
being slowly fouled by colloidal silica (20nm size). As expected from equations (5) and
(6) RF increases more rapidly at higher flux and the negligible rise at a flux of 15 implies
that this is below the critical flux of the particles. The CP rise tells a similar story except
the relative changes in CP are much more significant. The fouling phenomena illustrated
in Figure 4 required a steady increase in applied pressure. In this example the pressure
had to be increased by 30% , although the resistance increased by only 10% [7].
0.3 J = 15 J = 25 J = 30 3.5
J = 15
R f (X10 m )
-1

0.2 3.0 J = 25
2.5 J = 30
14

CP

0.1
2.0
0.0 1.5
-0.1 1.0
0 200 400 600 800 1000 0 200 400 600 800 1000

Run Time (mins) Run Time (mins)

Figure 4 Increases in cake resistance and concentration polarization due to silica particle
cake deposition as a function of imposed flux. ( Measured by salt pulse test {7]).

4. In Conclusion

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The Cake Enhanced Osmotic Effect is likely to be the primary cause of loss of
performance in RO desalting fouled by particulate deposits. Therefore any techniques
that can reduce the deposition have to be exploited. These include;
(i) effective pretreatment ~ to minimize CB;
(i) increasing the critical flux, JCrit, of the foulant species by,
~ improved mass transfer by enhanced and optimized hydrodynamics;
~ increasing particle size by aggregation of small particles;
~ enhancing backtransport by additional field forces.

The application of a non-uniform AC field in RO desalting could enhance critical flux if

it was able to promote aggregation of particulate foulants and/or provide an additional
backtransport velocity vector. Results reported in Parts C and D address these issues.

References

[1] Zydney,A.L. and Colton,C.K., A concentration polarization model for the filtrate flux
in crossflow microfiltration of particulate suspensions, Chem.Eng.Commun.,47,
pp 1-21 (1986)
[2] Li, H., Fane, A.G., Coster, A.G. and Vigneswaran, S., An assessment of
depolarisation models of crossflow microfiltration by direct observation through
the membrane, J.Memb.Sci. 172, pp 135-148 (2000)
[3] Coster,H.G.L., Electro-mechanics of particles in electric fields, Report Grahamtek,
October 2006.
[4] Neal, P.R.,H.Li., Fane,A.G., and Wiley, D.E., ‘ The effect of filament orientation on
critical flux and particle deposition in spacer-filled channels’, J.Memb.Sci., 214
,2, 165-178 ( 2003 )
[5] Schwinge,J., Neal.P.R., Wiley,D.E. and Fane ,A.G., ‘ Estimation of foulant deposition
across the leaf of a spiral-wound module’, Desalination, 146, 203-208 ( 2002 )
[6] Hoek,E. and Elimelech,M., Cake enhanced concentration polarization: A new
fouling mechanism for salt-rejecting membranes, Environ. Sci. Technol. 37
(2003) 5581 - 5588.
[7] Chong,T.H., Wong,F.S.and Fane,A.G., Enhanced concentration polarization by
unstirred fouling layers in RO: detection by stimulus-response technique.
J.Memb.Sci., 287 (2), 198-210 (2007)