DESALINATION

Desalination 113 (1997) 65-71

Compact accelerated precipitation softening (CAPS)
as a pretreatment for membrane desalination
I. Softening by NaOH
0. Kedema*, G. Zalmonb
a Weizmann Institute of Science, Rehovot, Israel
bEcosoft Company, Israel
Received 2 April 1997; accepted 3 1 July 1997
Abstract
This study examines the application of compact accelerated precipitation softening (CAPS)-a previously
developed process-as a pretreatment for membrane desalination. In this CAPS process, rapid precipitation of
calcium carbonate is achieved by cake filtration. The importance of this pretreatment step lies in the fact that
softening (by NaOH in this case) facilitates an increase of the recovery ratio in membrane desalination by decreasing
the potential for scaling. In addition, CAPS serves as an effective filtration step, reducing both turbidity and the silt
density index and hence the potential for membrane fouling.
Keywords: Water softening; Pretreatment; Cake filtration; SD1
1. Introduction
In the desalination of brackish water by
reverse osmosis (RO) or electrodialysis (ED),
recovery is usually limited by scaling and fouling
of the membranes, since osmotic pressure of the
concentrate becomes the limiting factor only at
*Corresponding author. Present address: The Institutes
for Applied Research, Ben-Gurion University of the
Negev, Beer-Sheva 84105, Israel. Fax: +972 (7)
647-2969; E-mail: ok.bgu.mail.bgu.ac.il.
relatively high salinities. Similarly, in marginal
desalination and in demineralization of potable
water for power stations and industry, scaling
and/or fouling constitute the limiting factors.
Scale formation is thus detrimental in a variety of
processes [ 1,2]. The challenge to be faced in the
desalting of low-salinity water is to increase the
recovery by the suppression of scaling, without
increasing the burden of chemicals to be added.
In such a desalting process, the precipitation of
calcium carbonate is prevented by acidification,
001 l-9164/97/$09.50 0 1997 Elsevier Science B.V. All rights reserved
PIZ 001 l-9164(97)001 15-X
66
0. Kedem, G. Zalmon /Desalination I13 (I 997) 65-7/
leaving calcium sulfate as the main potentially
scale-forming mineral. Thus, if the feed water
could be partially softened before the desalting
step, the feasible concentration factor and hence
the recovery ratio could be increased. Such a
pretreatment step can be viable only if a compact
and environmentally acceptable softening process
is available. Neither of the traditional softening
processes- lime softening and ion exchange-
answers these requirements: Lime softening is
slow, requires extensive space, and generates a
cumbersome sludge. Ion exchange, which has
largely replaced lime softening because of its
clean and convenient operation, requires a salt
solution for regeneration, and it is currently felt
that the disposal of these regenerating solutions
may contribute significantly to salination of
groundwater. Membrane softening, i.e., the use of
nanotiltration membranes to retain calcium in
preference to sodium, was not shown to lead to
very high recovery.
These considerations led us to develop a
softening process [3], which we designated
compact accelerated precipitation softening
(CAPS). This process is a compact variation of
softening by lime or sodium hydroxide, applied in
cake filtration technology. During the
development of the process, it became evident
that co-precipitation and filtration also may
eliminate various contaminants. The results
presented here and in the companion paper [4]
suggest that CAPS used as a pretreatment for RO
may reduce both fouling and scaling of RO
membranes.
2. Accelerated precipitation of CaCO,
As is the case of all crystallization processes,
precipitation of CaC03 from a supersaturated
basic solution is determined by the rate of
nucleation or by the rate of crystal growth. Clean
supersaturated solutions may remain metastable
for prolonged periods. The addition of a solid and
presence of various solutes influences
precipitation. The kinetics of all relevant steps of
the crystallization of CaCO, have been studied in
detail by the group of Nanchollas and a number
of other workers [ 5-81,
For any softening process used for practical
applications, it is desirable to avoid metastability
and to approach equilibrium as fast as possible so
as to achieve, within practically reasonable
residence times, concentrations close to their
equilibrium values.
After the addition of a base to a solution
containing Ca(HCO&, the addition of CaCO,
would appear to be the natural way to provide
sites for crystal growth and thus to accelerate
precipitation. It was indeed found that the
precipitation rate was considerably enhanced by
the presence of a suspended CaCO, precipitate.
However, if the solid were separated out after a
contact time of minutes, a substantial part of the
Ca was removed, but the clear solution still
remained supersaturated. It was shown by
Graveland [9] that nucleation by other minerals is
more effective and that, with this nucleation, the
subsequent crystallization takes place along the
axis of fast crystal growth. This phenomenon has
been applied for the construction of large water
softening installations [IO].
Kedem and Ben-Dror have found that very
fast equilibration is obtained when the super-
saturated solution is filtered through a cake of
CaCO, [3]. Apparently, this fast process includes
secondary nucleation as well as crystal growth
[l 11, since the size distribution of the particles is
not drastically changed upon repeated tiltration-
with-crystallization through the same cake. In the
experiments described below, accelerated
precipitation was investigated on a laboratory
scale. A description of an industrial plant, which
is currently under testing, will be published
elsewhere.
3. Methods of precipitation
Three systems were tested: (1) A loop for
circulating and separating the suspended solid;
0. Kedem, G. Zalmon /Desalination 113 (1997) 65-71 67
(2) cake filtration under vacuum in a conven-
tional Buchner funnel; and (3) circulating slurry
and cake filtration in a filter tube.
3.1. Circulating slurry
A microfiltration membrane was clamped into
a flow-through cell (Fig. 1). A suspension of
CaCOs (3 wt%) was circulated along one side of
the membrane by means of a pump, and a
vacuum was applied to the other, i.e., down-
stream, surface of the membrane. The solution
removed from the downstream side of the
membrane was continuously replaced by the
same volume of supersaturated solution from a
separating funnel. The supersaturated solution
was prepared immediately before each
experiment by adding NaOH (various amounts)
to tap water.
3.2. Buchnerfiltration
A suspension containing 25 g of precipitated
CaCO, was filtered through Whatman No. 50
filter paper in a 90-mm Buchner funnel to form a
cake of a few millimeters. Supersaturated
solutions were then filtered through this cake.
3.3. Cake$ltration in filter tubes
For CAPS systems, filter tubes are prepared
from filter fabric by thermal sealing. A
suspension of small CaCO, crystals is circulated
under pressure. Hard water and NaOH solution
are continuously added to the reservoir in the
cycle. In this system, part of the precipitation
takes place in the suspension, and the remainder
during passage through the cake. In the current
experiments, a single tube of 700 cm2 filter area
was mounted in a shell. A 3% suspension of
CaCO, was circulated through a suitable reservoir
and the addition of base was controlled to give
the desired pH of the product.
I I
Fig. 1. Supersaturated solution is prepared in the
separating funnel (1). A slurry containing suspended
CaCO, is circulated by a pump (2) along the membrane
(3). Softened water is drawn off by vacuum into a vessel
(4).
4. Softening parameters
For control of the softening process, both
calcium and magnesium concentrations have to
be considered, since routine determinations are
carried out for the sum of calcium plus
magnesium. The magnesium concentration is
only slightly changed in the process by co-
precipitation with calcium carbonate. Thus, for a
given type of water, we have to know the
necessary reduction of total hardness, i.e.,
calcium + magnesium, and the final calcium
concentration required. This information is
readily translated into the required quantity of
base or, given the concentration of bicarbonate in
the water, the pH of the product if equilibrium is
reached. In practice, the product will always be at
least slightly oversaturated. The customary
measure for oversaturation is the saturation index
(SI), i.e., the difference between the measured pH
of the solution and the equilibrium pH,
corresponding to the given ion concentrations [ 11.
68 0. Kedem, G. Zalmon /Desalination I13 (I 997) 65-71
SI=pH- pH,
SD1 = lOO(t,- t,)lt,T
pHs =pK, - pK, +p[Ca2] +p[HCO,-] + 5pfm
where pH, is the equilibrium pH, K ,the second
dissociation constant of carbonic acid, KS the
solubility constant of calcium carbonate, and jn
represents the activity coefficients.
where q is the time required for filtration of a
given volume at the end of the testing period, t, is
the initial time, and T is the total testing period.
Under the conditions studied here:
pfm=A [JIl(l+-Jl)] - 0.31 (forZc0.5)
where I is the ionic strength. At 20C
Since it is essential to perform this test on line
to avoid distortion of results by bacterial growth
during transportation or storage of filtered water,
we required a large enough continuous source of
product water. Therefore, an SD1 unit of
sufficient size was constructed and attached to
our CAPS pilot plant so that water could be tested
before and after softening.
pK, = 8.45; pK2 = 10.38;pK2 - pK, = 1.93
6. Results and discussion
A = 0.506
6. I. Softening by NaOH
In practice, the relationship between [Ca2]
and pH is determined empirically in the process
itself, and SI is calculated. The value of SI
characterizes the process performance. Process
control is thus based on feedback from the pH of
the product rather than on the calculated amount
of alkali to be added to the feed water.
6.1.1. Circulating slurry
5. Silt density index
The results of this series of measurements are
given in Table 1. Comparison of results for Ca2+
plus M$+ before and after the process shows the
decrease of total hardness. The time of contact, t,,
between the supersaturated solution and the
suspended precipitate (Table 1) is related to the
total filtration time, f/, and the ratio between
circulating volume V, and total volume V, by the
following equation:
The turbidity of the softened water was
monitored and low values were obtained. Low
turbidity reflects removal of suspended solids and
possibly some colloids. However, practical
experience has shown that turbidity is not the best
measure for the fouling tendencies of a given
water source. The widely used silt density index
(SDI) [ 121 is a better means of evaluating foiling
potential.
t, = tf v/v,
In our system, V, = 140m1, and V, = 1.5 1; thus t, =
0.093 9.
6.1.2. Cake filtration in a Buchner funnel
To obtain the SDI, the feed water is filtered
through a standard 0.45-mm microfiltration
membrane, and the water flux is determined at
zero time and after 15 min. The relative increase
in time required for the passage of a given
volume per minute indicates the clogging
tendency of the tested source.
Table 2 shows results of softening with cake
filtration. The most striking finding was the low
residual concentration of calcium at a given pH,
in comparison with the results given in Table 1,
despite the much shorter residence time.
Although there was no way for direct
measurement of this time interval, the order of
magnitude, which is given by the filtration rate
Table 1
0. Kedem, G. Zalmon /Desalination 113 (1997) 65-71 69
Circulating sluny of CaCO,. Composition of tap water and filtrate after the addition of NaOH
Tap water
[Ca*+
+Mti+, PH
meq/l
[NaOH], meq/l Filtrate Contact time, s
[Ca2 + M$+], [Ca*],
P@+l> PH
meqll meq/l meq/l
5.90 7.36 1.0 4.47
5.90 7.36 1.2 3.90
6.58 1.4 4.47
6.7 7.2 2.0 3.41
6.58 2.2 3.26
6.58 2.83 2.05
Table 2
Cake filtration in a Buchner funnel. Composition of
softened water (filtrate) after addition of NaOH and cake
filtration
[Ca2+], meq/l [M$tl, meq/l PH
5.21 1.78 7.4
3.73 1.67 8.1
3.06 1.58 8.0
2.15 1.63 8.2
1.50 1.58 8.2
1.12 1.60 8.3
1.07 1.64 8.4
0.73 1.57 8.5
0.54 1.54 8.7
and the thickness of the cake layer, is limited to a
few seconds. Clearly, the contact between the
supersaturated solution and the crystals in the
cake is very effective. Thus, cake filtration is
more effective than crystallization on a
circulating slurry.
61.3. Cake filtration in aJilter tube
In contrast to the experiments described
above, water treatment in the single tube was
carried out as a continuous process. The pH of the
filtered product was monitored, and the addition
of base to the hard water was regulated by
feedback from the pH of the filtered solution.
3.11 1.36 8.1 17.3
2.61 1.37 8.20 15.4
3.03 1.44 -
- -
8.20 32
1.81 1.45 8.5 25.2
0.61 1.44 9.20 31.7
In the experiments described in Tables 1 and
2, partial softening was carried out, as is desirable
for the treatment of drinking water. The upper
limit of the pH was kept in the limits required for
this purpose. Table 3 shows the parameters for
continuous softening to a similar residual
hardness.
For the application of CAPS as pretreatment
for membrane desalting, the calcium concen-
tration has to be reduced to much lower values.
The relationship between the product pH and
residual calcium in the product water is shown in
Table 4. We chose a final Ca2+ concentration of
~0.3 meq/l, and hence a pH of 9.0. Table 5 gives
the parameters for softening at this pH.
Tap water is normally slightly supersaturated.
As pointed out above, in principle, the softened
water must also be slightly oversaturated, as is
any supernatant after precipitation. The super-
saturation is, in fact, low, although the overall
residence time of the solution in the plant is short,
and the contact time between solution and cake at
the approach to equilibration is only a few
seconds. Table 5 shows that the saturation index
of the hard water and the softened water are quite
similar. However, the amount of precipitate that
would be created upon equilibration is much
smaller in the softened water.
For desalting following the softening, the
important parameter is the concentration of
calcium. Before concentration by RO can be
70 0. Kedem, G. Zalmon /Desalination 113 (1997) 65-71
Table 3
Table 5
Parameters of CAPS-treated tap water, pH 8.3
Parameters of CAPS-treated tap water, pH 9.00
Parameter Experiment 1 Experiment 2
Tap
Product
Tap
Product
water water
D2+l,
5.42 1.52 5.4 1.72
meq/l
[Ca] +M82+], 6.88 3.00 6.98 3.00
meq/l
WO,l>
3.936 2.282 3.85 2.312
meq/l
[WI, -
0.144 - 0.156
meq/l
Conductivity, 926.6 806.4 924.6 812.2
@/cm
PH
7.58 8.29 7.4 8.31
SI 0.58 0.49 0.28 0.22
Parameter Experiment 1
Tap
Product
water
Experiment 2
Tap
Product
water
CCa2+l,
5.88
meq/l
[Ca2] + MC], 7.68
meq/l
WOjl>
4.05
meqil
w:ml> -
meq/l
Conductivity, 986
j_Slcm
PH
7.39
Temp., C 24.9
Turbidity, -
NTU
SI 0.36
0.26 5.68 0.3
1.86 7.62 1.82
1.63 4.06 1.68
0.29 0.32
817 996 832
9.02 7.25 9.00
31.2 25.3 30.2
0.05 0.11
0.28 0.26 0.32
Table 4
Influence of pH on water hardness. Feed water alkalinity:
4.06 meq/l
Flow Vmin:
PH
[Ca2 + M?], meq/l [Ca2+], meq/l
7.39 7.65 5.8
8.3 2.98 1.34
8.49 2.4
-
8.82 2.12
-
9.00 1.82 0.28
9.27 1.61 0.17
9.5 1.54 0.11
9.76 1.44 0.03
10.01 1.34 ND
Recycle 8.7 9.3
Product 0.6 0.8
carried out, the water has, of course, to be
acidified, and then the concentrations of sulfate
and calcium become decisive for the maximal
concentration factor. The concentrations of
bicarbonate and carbonate after softening given in
Table 5 require less acid than hard water for
stoichiometric acidification. If ED is applied for
the desalting, even less acid is consumed, since
for this process only the brine is acidified to a pH
that prevents precipitation of carbonate.
Table 6
SD1 of tap water and softened water
Tap water Treated water
SD1
PH
[Ca2+], meq/l SD1
1.65 8.30 1.56 0.38
1.95 8.29 1.72 0.42
3.04 8.31 1.64 1.05
3.48 8.30 1.66 1.07
3.18 8.28 1.64 1.10
2.05 9.01 0.26 0.61
2.45 8.98 0.30 0.70
6.2. Silt density index
The tap water used in our experiments was
obtained from wells with very clear water.
Table 6 shows the change in SD1 effected by the
CAPS softening. Even though the values for tap
0. Kedem, G. Zalmon /Desalination 113 (I 997) 65-71 71
water fluctuated, and the correlation between the
degree of softening and the decrease of SD1 was
not clear cut, it was consistently found, as is
evident from the table, that the softening
decreased the SDI, and hence the clogging
tendency of the product water.
7. Conclusions
CAPS combines compact softening with
effective filtration. Cake filtration facilitates fast
equilibration between solution and precipitate. In
addition, co-precipitation and/or adsorption
remove other suspended and dissolved sub-
stances. This is shown by decreased turbidity and
SDI. It is predicted that as a pretreatment for RO
or ED, CAPS should lead to increased recovery,
since both scaling and fouling will be suppressed.
CAPS will be economically feasible if it can
replace more extensive pretreatment technologies.
This can be evaluated only in field trials
In this study, we concentrated on the treatment
of potable water used in the production of process
water. Water from other sources will be studied in
the future.
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