DESALINATION

ELSEVIER Desalination 165 (2004) 283-288

www.elsevier.com/locate/desal

Saving water in a volume-decreasing diafiltration process

Darko M. Krstid, Miodrag N. Tekid*, Zoltan Z. Zavargo, Mirjana S. Djurid,
Gordana M. l~irid
Faculty of Technology, University of Novi Sad, Bulevar Cara Lazara 1, 21000 Novi Sad, Serbia and Montenegro
Fax +381 (21) 450413; email: dakrstic@eunet.yu (M.N. Tekic)

Received 20 January 2004; accepted 2 February 2004

Abstract
The aim of this work is to improve a mathematical model to describe the volume-decreasing diafiltration process
by including macrosolute rejection. Water consumption in this continuous process was analyzed and a significant
advantage when comparing both the classical diafiltration process and multi-stage diafiltration processes was noticed.
For whey protein, a relative volume was used continuously. A decreasing diafiltration process was estimated at a level
of 1.36, while the corresponding values of fresh water relative volumes were reported as follows: 5.4 for the classical
process, 2.9 for the two-stage process and 1.5 for the six-stage diafiltration process.

Keywords: Volume-decreasing diafiltration; Mathematical modelling; Saving water

I. Introduction
Ultrafiltration (UF) has been used widely for
over two decades as an application for separation
in food processing, the chemical industry and in
biotechnology. In many circumstances UF has
several advantages over other separation tech-
niques such as distillation, extraction, evapo-
ration, and centrifugation.
*Corresponding author.
In order to achieve a high level o f macro--
microsolute separation, UF is frequently coupled
with diafiltration [1]. The diafiltration process
requires the addition o f pure solvent, usually
water, to the feed and can be applied to both
continuous or batch UF. The classical process of
macrosolute concentration, followed by removal
of impurities (microsolutes), consists of several
phases: (1) UF to concentrate macrosolute,
(2) diafiltration to "wash out" microsolute by a
pure solvent introduced into the system, and

Presented at the EuroMed 2004 conference on Desalination Strategies in South Mediterranean Countries: Cooperation
between Mediterranean Countries of Europe and the Southern Rim of the Mediterranean. Sponsored by the European
Desalination Society and Office National de l'Eau Potable, Marrakech, Morocco, 30 May--2 ,,rune, 2004.
0011-9164/04/$- See front matter © 2004 Elsevier B.V. All rights reserved
doi; 10.1016/j.desal.2004.06.033
284 D.M. Krstid et aL / Desalination 165 (2004) 283-288

(3) UF to concentrate the macrosolute to the final Pure solvent, QD Retentate

concentration. Jaffrin and Charrier [2] proposed
a continuous diafiltration process in which pure
solvent is continuously added at a flow rate lower
than the permeate flow rate so that concentration
of macrosolute occurs simultaneously with the Feed
tank

g
washing out of the microsolute. Although the
process consists of a single diafiltration phase, the
continuous decrease of volume results in simul-
taneous reaching of final concentrations of both
macro- and microsolute. It should be emphasized
that the volume-decreasing diafiltration requires
less washing liquid than the constant volume
diafiltration for the same concentration and
purification factors. This is an advantage that
Permeate, QF I
might be of essential importance for the process Fig. 1. Schematic diagram of volume-decreasing
to have practical application. diafiltration.
Jaffrin and Charrier [2] analyzed the process
in which macrosolute rejection coefficient was 1.
However, such an approach is a kind of ideali- Since the final volume is smaller than the ini-
zation, and it is clear that, in a real system, some tial one, the pure solvent flow rate Qo must be a
permeability of macrosolute must occur. Thus, fraction of permeate flow rate QF, i.e., their
the aim of this work is to introduce the macro- relation can be expressed as:
solute rejection into a model of volume-
decreasing diafiltration. Moreover, a significant Qn = ~ QF (2)
advantage of the volume-decreasing diafiltration
process concerning water conservation is dis- where ot < 1 and represents a volume decreasing
cussed. Water consumption in a continuous ratio. It is obvious that Eq. (2) defines a series of
process, related to the volume-decreasing ratio, processes; each of them is characterized by its
was compared with water consumption in own ~t value.
classical as well as multi-stage processes. The mass balance of macrosolute can be
expressed in terms of its concentration as well as
rejection coefficient, which cannot be neglected
2. Modelling of the volume-decreasing diafil- for a real process considered in this paper:
tration process
A simplified scheme ofa diafiltration process, d(VC) _ Qp c(1 -R) (3)
occurring under the condition of decreasing dt
volume, is presented in Fig. 1. In such a process
the volume changes in time according to the Rearranging the Eq. (3) gives:
relation:
QF(1-R) d t - ~ d ( l n V )
dV
dt- QD - QF (1)
fCl d(lnC)=-ftl V d (4)
co o vo
 D.M. Krsti6 et al. / Desalination 165 (2004) 283-288 285

Having in mind that actual volume can be [ In Cf 1-1

given by the Eq. (5): Co
tz = [1 + l (9)
V= Vo-QF(1-~)t (5) In c_£
c:
and assuming that the permeate flux remains
unchanged during the process, all integrals in However, in the case where the rejection of both
Eq. (4) can be solved analytically [3]. In this way macro- and microsolute cannot be neglected, a is
a relation is obtained, which can serve to express defined as presented in our previous paper [3]:
the concentration factor:
Rln c° +rln Cf
c: _ {[1 (1-~)J.A t: -' (6)
~= c: CO
(lo)
Co Vo In Cs + In c°
co c:
The same relation can be used to express
processing time that will guarantee obtaining the Once chosen, the volume decreasing ratio (tx) is
product with adequate concentration of the easy to control by measuring the permeate fluxes
macrosolute: and related adjusting of the valve at the fresh
water pipe.
It can be expected that a volume-decreasing
= [1_( Co ] R£~-~] Vo (7) process will lead to the saving of fresh water
tf [ ~ Cf ) (1-a)'J'A added to the system. This is a significant advan-
tage as the amount of the required water has a
Alternatively, Eq. (7) can be given related to the great influence on the cost of the entire operation.
purification factor, having in mind the existing The advantage can be proved by comparison of
relation between the purification factor and con- water consumption of both classical diafiltration
centrations of macrosolute: with constant volume and diafiltration with
decreasing volume. The relative volume of water
Co_ Co R----~ in classical diafiltration process is:
(8)
c:
~co,~t = -VD c°
- = In -- (11)
vo c:
3. Water consumption in a volume-decreasing
or
diafiltration process
The suggested continuous process shown in ~co,~,- VD - 1 In c---Z° (12)
Fig. 1, consisting of simultaneous UF and dia- vo 1-r c:
filtration, is elegant and easy to control. A very
important parameter of the process is the volume for the case when a membrane rejects a certain
decreasing ratio (a), which should be chosen amount of microsolute.
related to the desired concentration and purifica- On the other hand, the volume of the added
tion factors. In an ideal case (R = 1, r = 0), tt is water during volume-decreasing diafiltration can
defined, according to Jaffrin and Charrier [2], as: be expressed as:
286 D.M. Krstid et aL / Desalination 165 (2004) 283-288

9 (13) Table 1
Data used for water consumption comparison [5]
Combining Eqs. (7) and (13) gives a relative
volume of fresh water related to the volume Quanti~ Va~e
decreasing ratio, concentration factor and rejec- C? % 95.5
tion coefficient [3] as presented by Eq. (14): Co, gL -j 7.7
cggL -I 3
Co, g L-1 43
R 0.99
(14) r 0.07

Co ) 11
When considering saving water, it is necessary
Table 2
Comparison of water consumption in diafiltration
processes
to mention multi-stage diafiltration processes
consisting of particular stages connected by co- Purification factor, Co/cI 43/3
Water consumption, 13:
current or counter-current streams of working
Classical diafiltration 5.4
fluids. Recently, Barba et al. [4,5] suggested an Two-stage diafiltration 2.9
interesting idea for the water conservation Six-stage diafiltration 1.5
problem by using a two-stage diafiltration process Volume-decreasingdiafiltration:
for the production of whey protein concentrate. 13 1.37
Additional positive effects were achieved by t~ 0.58
using the diluted solution (permeate) in the first
stage of removing microsolutes, which, on the
other hand, limits the final concentration of
microsolute to the permeate concentration. Fresh
water is used only in the second (final) stage of
the process. Same authors have discussed pro-
I a=0.8
cesses with up to six stages.
Using the data presented in Table 1 [5], a
relative volume of fresh water as a function of
2 ~=0.7
both the concentration factor and volume-
decreasing ratio was calculated as if the whey
proteins were concentrated in volume-decreasing
diafiltration. The values of the volume-decreasing
ratio were calculated by using Eq. (10) while the
relative volume values were estimated by using
Eq. (14). The dependence of the fresh water
0 20 40 60 80 100 120 140
relative volume of the concentration factor for
various volume-decreasing ratios is presented in
c,/Co
Fig. 2. Fig. 2. Relative volume of fresh water vs. concentration
For a comparison of water consumption in all factor in a volume-decreasing process at different
mentioned processes, the values of relative volume-decreasingratios.
 D.M. Krsti6 et al. / Desalination 165 (2004) 283-288 287

volumes of fresh water for classical, two-stage, necessary value of tt was estimated using Eq. (10)
six-stage diafiltration processes are taken from in which the data from Table ! were substituted.
the work of Barba et al. [5], while the con- The comparison clearly shows an advantage of
sumption for a continuous volume-decreasing volume-decreasing diafiltration, which seems to
process was estimated by applying Eq. (14). The spend less water than six-stage diafiltration, as
can be seen in Fig. 3 and Table 2.
Finally, the influence ofmacrosolute rejection
6
5.4 by membrane to the water consumption was
analyzed. It was concluded that a decrease of the
5-
rejection coefficient causes a faster increase in
water consumption during concentration, which
can be seen in Fig. 4.
" 2.9
>3 '"'"
II ..'"' .0.,'"
4. Conclusions
1.5 . ,-.-
,..,- , .......... .....
The process model of volume-decreasing
diafiltration was improved by including the
1 ."'i,,,::::::': ............ 7 ' "
rejection of both macrosolutes and microsolutes,
o 4O, .... necessary in any real diafiltration process. Thus,
0 20 40 60 80 100 120 140 the approach given by Jaffrin and Charrier [2]
c,/Co was improved, getting a more realistic character.
Fig. 3. Comparison of water consumption in the It was also demonstrated that the analyzed
volume-decreasing diafiltration process with water volume-decreasing diafiltration process consumes
consumption in classical (one-stage), two-stage and six- much less fresh water than classical diafiltration
stage diafiltration processes. as well as the multi-stage diafiltration processes.
There is no doubt that the continuous process
1.52 deserves attention and offers some opportunities
that should be investigated in more detail.
1.50- (~¢=0.6
'

1,48. - .9~
5. Symbols
~1.46
~" ( / R=0.8 A Membrane area, m 2
R=0.7 C Concentration ofmacrosolute at any
1.44-
time, kg m -3
1A2- C Concentration ofmicrosolute at any
time, kg m -3
1.40 co - -
Initial concentration ofmacrosolute,
6 4:060 801b0120140 kg m -3
c,/Co Co m Initial concentration ofmicrosolute,
Fig. 4. Relative volume of fresh water vs. concentration kg m -3
factor in a volume-decreasing process for various -
Final concentration of macrosolute,
rejection coefficients ofmacrosolutes. kg m -3
288 D.M. Krsti6 et aL / Desalination 165 (2004) 283-288

cf - - Final concentration o f microsolute, A c k n o w l e d g e m e n t

kg m -3
J -- Permeate flux, m 3 m -2 h- The Ministry for Science, Technology and
-- Pure solvent flow rate added during Development, Republic o f Serbia, supported this
diafiltration, m 3 h- research (Project No 1362).
-- Permeate flow rate, m 3 h-
R Macrosolute rejection coefficient
References
r - - Microsolute rejection coefficient
t - - Processing time, h [ 1] B. Dutre and G. Tragardh, Macrosolute-microsolute
V -- Volume in the tank at any time, m 3 separation by ultrafiltration: A review ofdiafiltration
Vo - - Initial volume in the tank, m 3 process and applications, Desalination, 95 (1994)
-- Pure solvent volume added during 227-267.
diafiltration, m 3 [2] M.Y. Jaffrin and J.Ph. Charrier, Optimization of
ultrafiltration and diafiltration processes for albumin
Greek production, J. Membr. Sci., 97 (1994) 71-81.
[3] M.N. Teki6, Z.Z. Zavargo, D.M. Krsti6 and M.S.
- - Volume-decreasing ratio defined by Djuri6, Mathematical model of variable volume dia-
Eq. (2) filtration, Hung. J. Indus. Chem., 30 (2002) 211-214.
[~COrISt - - Relative volume o f water in the [4] D. Barba, F. Beolchini and F. Veglio, Water saving
classical process in a two stage diafiltration for the production of
whey protein concentrates, Desalination, 119 (1998)
3var - - Relative volume o f water in the
187-188.
volume-decreasing process
[5] D. Barba, F. Beolchini and F. Veglio, Minimizing
water use in diafiltration of whey protein concen-
gates, Sep. Sei. Technol., 35 (2000) 951-965.