See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/241090019

Electrochemical removal of calcium and magnesium ions from aqueous

solutions

Article  in  Desalination · August 2011

DOI: 10.1016/j.desal.2011.04.005

CITATIONS READS

25 1,526

1 author:

Kai Zeppenfeld
University of Münster
35 PUBLICATIONS   163 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

CaCO3 precipitation at different water flow View project

All content following this page was uploaded by Kai Zeppenfeld on 08 October 2017.

The user has requested enhancement of the downloaded file.

This article appeared in a journal published by Elsevier. The attached
copy is furnished to the author for internal non-commercial research
and education use, including for instruction at the authors institution
and sharing with colleagues.
Other uses, including reproduction and distribution, or selling or
licensing copies, or posting to personal, institutional or third party
websites are prohibited.
In most cases authors are permitted to post their version of the
article (e.g. in Word or Tex form) to their personal website or
institutional repository. Authors requiring further information
regarding Elsevier’s archiving and manuscript policies are
encouraged to visit:
http://www.elsevier.com/copyright
 Author's personal copy

Desalination 277 (2011) 99–105

Contents lists available at ScienceDirect

Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Electrochemical removal of calcium and magnesium ions from aqueous solutions

Kai Zeppenfeld ⁎
Schottlandstr. 4a, D-59368 Werne, Germany

a r t i c l e i n f o a b s t r a c t

Article history: The present study shows upon, electrochemical removal of Ca2+ and Mg2+ ions from aqueous solutions.
Received 24 January 2011 Calcite and brucite precipitation occurs through a chemical process following the electrochemical generation
Received in revised form 30 March 2011 of OH− ions in the vicinity of the electrode surface. The kinetics of the electrochemical calcite and brucite
Accepted 1 April 2011
precipitation were examined by measuring the electric conductivity as a function of time using different
Available online 22 April 2011
voltages and concentrations. The electric current density initially augments the electrochemical precipitation
Keywords:
of calcite, but at a sufficiently higher current density the precipitation rate tends to an asymptotic limit.
Water softening Furthermore, the precipitation rate of calcite is limited by diffusion kinetics of HCO−3 ions and does not vary

Electrochemical precipitation with the Ca2+ concentration. In contrast, the electrochemical precipitation of brucite correlates with current
Calcite density, as there are no limitations in diffusion kinetics. With increasing Mg2+ concentration the rate constant
Brucite of brucite decreases as small Mg2+ concentrations or high pH values promote the generation of MgOH+(aq.)
Energy consumption species in the reaction zone, which are responsible for an enhanced precipitation rate. In addition the specific
energy consumption required for 1 mmol/L Ca2+ removal strongly increases with the applied voltage,
whereas the energy consumption required for 1 mmol/L Mg2+ removal is nearly independent of the applied
voltage.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction is reduced on the cathode in a potential range U between −0.8 and

−1.2 V by following electrochemical reaction:
It is becoming increasingly difficult to provide water of a suitable
− −
quality for all application purposes at home and in industry. 2 H2 O þ O2 þ 4 e → 4 OH ð1Þ
This concerns in particular the hardness of the water, i.e. water with
When the applied potential is more negative (U b − 1.23 V) water
a high content of calcium and magnesium ions, which causes scale
is directly reduced to:
deposits of calcium carbonate (CaCO3) and magnesium compounds
(Mg(OH)2, MgCO3, Mg4(CO3)3(OH)2 3H2O). The precipitation and − −
2 H2 O þ 2 e → H2 þ 2 OH ð2Þ
crystallization of these insoluble salts causes a decrease in the flow
rate in pipes and reduce heat transfer in heat exchangers. Various The generation of OH− ions, either by reaction (1) or reaction
methods are used to prevent scaling, for example by acidification of (2), acts to convert the hydrogen carbonate ions HCO−
3 into carbonate
the water, by forcing the precipitation by some chemical process, by ions CO2−3 by following the chemical reaction:
using exchange resins, or by membrane techniques, e.g. reverse
− − 2−
osmosis and nanofiltration [1]. Another option is adding chemical HCO3 þ OH → CO3 þ H2 O ð3Þ
inhibitors. They can prevent the precipitation of scale forming salts by
In a third step, the carbonate ions may react with calcium ions as a
adsorption on the crystallization surface, thereby delaying nucleation
critical supersaturation Scalcite is achieved and calcium carbonate
and reducing the precipitation rate [2].
CaCO3 (s) is deposited on the electrode surface:
Additional methods include electrochemical precipitation pro-
cesses in which OH− ions are created with the help of electrodes and a 2þ 2−
Ca þ CO3 → CaCO3ðsÞ ð4Þ
sufficiently high flow of electric current is present in the vicinity of the
electrode surface [3–10]. During water electrolysis, dissolved oxygen The supersaturation Scalcite is defined by

  
Ca2þ CO2
3
⁎ Tel.: + 49 2899 927458; fax: + 49 2389 533662. Scalcite ¼ ð5Þ
E-mail address: drkaizepp@t-online.de. Kso

0011-9164/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.04.005
 Author's personal copy
100 K. Zeppenfeld / Desalination 277 (2011) 99–105
where (Ca2+) and (CO2− 3 ) are the ionic activities and Kso is the
thermodynamic solubility product of calcite (pKso = 8.42).
The high pH conditions in the vicinity of the cathode also promote
the precipitation of magnesium hydroxide Mg(OH)2 as a critical
supersaturation Sbrucite is achieved:
2þ −
Mg þ 2 OH → MgðOHÞ2
The supersaturation Sbrucite is defined by
 
2þ  2
Mg ðOH Þ
Sbrucite =
Kso
where (Mg2+) and (OH−) are the ionic activities and Kso is the
thermodynamic solubility product of brucite (pKso = 11.16).
The electrochemical method for reducing the hardness of water
offers many advantages, e.g. environmental compatibility, avoidance
of any addition of chemicals, accessibility to automation and
convenient process control. The main factors preventing the use of
the electrochemical technology in desalination applications is the
very high specific electrode area requirement and the high energy
consumption. For instance, in a brackish desalination plant with a
calcium concentration of around 2000 ppm and a flow rate in order of
20 m3/h, an electrode area of 400 m2 is required to precipitate 20 kg/h
CaCO3. Thus the maximum specific energy consumption is 16 kWh
per kg CaCO3 [8,10].
In the current study the electrochemical precipitation of CaCO3 and
Mg(OH)2 were measured as a function of time for different applied
voltages in pure Ca(HCO3)2 and Mg(HCO3)2 solutions with different
concentrations. The laboratory results obtained may provide a better
understanding of the electrochemical precipitation processes, which
can be considered as a good simulation of an industrial application.
2. Experimental
Ca(HCO3)2 and Mg(HCO3)2 solutions were prepared by dissolution
of known quantities from corresponding reagent grade crystalline
solids (Merck) of CaCO3 and MgCO3 in CO2–H2O mixtures. H2O was
deionised water (0.08 μS/cm) and CO2 was gaseous (99.8%). Next, the
pH (measured by a WTW 320 pH meter, Merck Labor und Chemie
Vertrieb West GmbH, Bochum, Germany) was adjusted to 7.0 by
bubbling air through the solutions. The temperature of all solutions
was 25 ± 0.5 °C as the room temperature was kept constant. The
electric conductivity was measured by a WTW 318 instrument (Merck
Labor und Chemie Vertrieb West GmbH, Bochum, Germany). Table 1
shows the five Ca2+ and Mg2+ concentrations C and the electric
conductivity κ25 of the solutions. The Ca2+ and Mg2+ concentrations
were selected so that the values for κ25 were identical. The ion
concentration C of the solutions is proportional to their electric
conductivity κ25:
κ25 = Λmolar C
By measuring the electric conductivity as a function of the Ca2+
and Mg2+ concentrations C the average molar equivalent conductivity
Table 1
Electric conductivity κ25, the Ca2+ and Mg2+ concentrations C of the prepared Ca
(HCO3)2 and Mg(HCO3)2 solutions at pH 7.0.
κ25 (mS/cm) C Ca2+ (mmol/L) C Mg2+ (mmol/L)
0.300 1.67 1.72
0.400 2.22 2.30
0.600 3.33 3.45
0.800 4.44 4.60
1.000 5.55 5.75
Λ molar can be calculated. A value of 180 ± 3 Scm2/mol was calculated
for the Ca(HCO3)2 solutions and 174 ± 3 Scm2/mol for the Mg(HCO3)2
solutions, respectively. These values of Λ molar are in accordance with
the literature [11]. The low concentration dependency of Λ molar [12],
causing an error of ± 3 Scm2/mol was neglected. An additional low
dependency on dissolved CO2 on the conductivity measurements,
ð6Þ with a maximal error of 2% [13] was also neglected.
Two hundred mL of each Ca(HCO3)2 and Mg(HCO3)2 solution
(Table 1) was added to a 300 cm3 glass vessel. A stainless steel plate
(length 10.0 cm, width 5.0 cm) was used as cathode and a grid of
titanium cast iridium oxide (length 10.0 cm, width 5.0 cm) was used
ð7Þ
as anode. Both electrodes were immersed precisely 5.0 cm into the
solution. The inter electrode distance was 0.5 cm. The solution was
stirred continuously (500 rpm) using a magnetic stirrer. With the help
of a DC supply various voltages between 3.0 V and 16.0 V were applied
to the electrodes.
The precipitation of CaCO3 (Eq. (3) and Eq. (4)) and Mg(OH)2
(Eq. (6)) causes a alternation of the concentrations |Δ| in the solutions
and can be described as follows:
2+
jΔCaðHCO3 Þ2 j = jΔCaCO3 j = jΔCa j ð9Þ
jΔMgðHCO3 Þ2 j = jΔMgðOHÞ2 j = jΔMg
2+
j ð10Þ
In order to examine the reduction |Δ| of the Ca2+ and Mg2+
concentrations C occurring during electrolysis, the electric conduc-
tivity κ25 of the solutions was measured as a function of time (Eq. (8)).
Furthermore the electric current Iz could be determined because a
reduction in the concentration C is correlated with a reduction of
the electric current. The plot of the dependence of the calculated
current density I (A/m2) measured at the beginning of each ex-
periment as a function of the applied voltage U (V) for the five
different values of the electric conductivity κ25 (Table 1) is shown in
Fig. 1. The experimental data demonstrate that the U versus I function
is linear, whereby the current density I increases with increasing
applied voltage and increasing conductivity, respectively. This is in
line with Ohms law:
1 d
U= I ð11Þ
κ25 A
in which d (0.5 cm) is the inter electrode distance and A (25.0 cm2)
the immersed area of the cathode. The cathode surface is never
completely blocked by the scale forming salts because of the
300
0.3 mS/cm
250 0.4 mS/cm
0.6 mS/cm
ð8Þ 200 0.8 ms/cm
I (A/m2)
1.0 mS/cm
150
100
50
0
0 4 8 12 16 20
U (V)
Fig. 1. The current density I (A/m2) measured at the beginning of the electrolysis as a
function of the applied voltage U (V) for the different electric conductivities κ25 of the
solutions.
 Author's personal copy

K. Zeppenfeld / Desalination 277 (2011) 99–105 101

formation of hydrogen bubbles onto the metal (Eq. (2)). In addition,
random fluctuations of the current density were clearly related to the
spontaneous detachment of flakes under the effect of the hydrogen
pressure. This allows a quasi continuous precipitation of scale forming
salts by the self generation of the surface [7]. A weak increase of the
temperature with time, max. 3 °C on the dependence of the
conductivity measurements was neglected.
After terminating the electrolysis the white crystalline precipita-
tion products were removed from the electrode, dried at room
temperature, and examined by X-ray powder diffractometry. The
diffraction spectra shows that the precipitate of the Ca(HCO3)2
solution consisted only of calcite (CaCO3), while the precipitate of
the Mg(HCO3)2 solution consisted only of brucite (Mg(OH)2).
3. Results and discussion
3.1. Precipitation kinetics
Fig. 2 shows the time related Ca2+ and Mg2+ concentrations C for a
3.33 mmol/L Ca(HCO3)2 and a 3.45 mmol/L Mg(HCO3)2 solution
respectively. The electric conductivity κ25 for both solutions is
0.600 mS/cm. The applied voltage is 6.0 V, while the measured
electric current Iz at the beginning of the experiment is 0.088 A.
Therefore the current density I can be calculated to 35.2 A/m2 (Fig. 1).
The concentration values showed a strongly declining tendency with
time t, as calcite and brucite is precipitated on the cathode. The
precipitation follows a rate expression of the form
−dC = dt = k C
where k (1/min) is the rate constant of precipitation. Analysis of
CaCO3 and Mg(OH)2 crystal growth data is facilitated by the
integrated form of Eq. (12):
ln C0 − ln C = k t ð13Þ
with C0 is the concentration of Ca2+ and Mg2+ ions before
precipitation is started and C is the Ca2+ and Mg2+ concentration
measured at time t. The linear plot of ln C0 − ln C versus time
presented in Fig. 2 is valid to explain the experimental results. For the
Ca(HCO3)2 solution and the Mg(HCO3)2 solution k could be calculated
to (25.8 ± 0.3) 10− 3 (1/min) and (5.7 ± 0.1 10− 3) (1/min), respec-
tively. However Eq. (12) and Eq. (13) are restricted to a stoichiometric
solution composition. The growth rate of calcite and brucite may also
be affected by the aqueous composition through the anion to metal
cation concentration ratio of the solution [14–16].
3.2. Electrochemical Ca2+ removal
Fig. 3 shows the experimental rate constant k, or the electro-
chemical precipitation rate of calcite as a function of the current
density I (A/m2), for the five different Ca2+ concentrations listed in
Table 1. With increasing I, the OH− quantities ((Eq. (1) and Eq. (2))
produced at the cathode increases according to Faradays law. As a
result the current density initially augments the precipitation but at a
certain high current density the precipitation rate tends to reach a
limit. This phenomenon has been observed in other studies [5,7,8,10].
Therefore in Fig. 3 the values of the reciprocal rate constant 1/k are
ð12Þ plotted as a function of 1/I. The linear dependence corresponds to an
equation in the form of

4
1 = k = mCa = I + 1 = kðI→∞Þ ð14Þ

3 in which mCa is the slope of the straight lines and k(I→∞) denotes the
extrapolated rate constant at I → ∞. According to Eq.(14) the limiting
C (mmol/L)

value of the electrochemical precipitation rate could be calculated as

k(I→∞) = (44.6 ± 0.6) 10− 3 (1/min). This value is valid for the
2
measured Ca2+ concentration range. A plot of mCa calculated by
linear regression at the five different Ca2+ concentrations is shown in
Fig. 4. It is clear that mCa does not vary with the Ca2+ concentration,
1
Calcium
and an average value of mCa = (6.0 ± 0.2) 102 (minA/m2) was
determined.
Magnesium
In aqueous solution the calcite growth rate is strongly dependent
0 on the supersaturation Scalcite expressed by Eq. (5). With increasing
0 10 20 30 40 50 Scalcite the precipitation rate r follows an expression of the form
15 r ~ (Scalcite − 1)x. Therefore r corresponds to a linear (x = 1) [17–19]
Calcium or parabolic dependence (x = 2) [20–22] on the degree of super-
saturation. In contrast, the electrochemical precipitation rate k
12 Magnesium
increases initially with increasing current density and increasing
OH− concentration, respectively. Higher current densities have no
(ln Co - ln C) 10-1

9 considerable influence on the precipitation rate, which was demon-

strated by Eq. (14). Gabrielli et al. [7] suggested that limitations in the
mass transfer rate of Ca2+ and HCO− 3 ions from the solution bulk to
6 the very vicinity of the cathode are responsible for the asymptotic
precipitation tendency. This is supported by the fact that the
precipitation rate does not vary with the Ca2+ concentration (Fig. 3
3
and Fig. 4). Therefore reaction (3) is limited by diffusion kinetics of
the negative HCO− 3 from the solution bulk towards the negative
0 reaction zone (cathode). At high current densities and consequently
0 10 20 30 40 50 high OH− concentrations, reaction (3) is the rate limiting step for
t (min) electrochemical calcite precipitation. It can be suggested that reaction
(4) is fast as the limited CO2− 3 concentration in the reaction zone
Fig. 2. Time versus the Ca2+ and Mg2+ concentrations C (top) and the parameter
ln C0 − ln C versus time (bottom) for two solutions with 3.33 mmol/L Ca2+ and
determines the electrochemical precipitation rate. Therefore the
3.45 mmol/L Mg2+, an electric conductivity of 0.600 mS/cm and an applied voltage precipitation rate does not vary with the Ca2+ concentration in the
of 6.0 V. measured concentration range. Thus the resulting supersaturation
 Author's personal copy

102 K. Zeppenfeld / Desalination 277 (2011) 99–105

20
40 1.67 mmol/L 1.67 mmol/L

1/k 101 (min)

k 10-3 (1/min)
15
30
20 10

10 5

0 0
0 50 100 150 200 250 0 5 10 15 20 25 30
20
40 2.22 mmol/L 2.22 mmol/L

1/k 101 (min)

k 10-3 (1/min)

15
30
20 10

10 5

0 0
0 50 100 150 200 250 0 5 10 15 20 25 30
20
40 3.33 mmol/L 3.33 mmol/L

1/k 101 (min)

k 10-3 (1/min)

15
30
20 10

10 5

0 0
0 50 100 150 200 250 0 5 10 15 20 25 30
20
40 4.44 mmol/L 5.55 mmol/L
1/k 101 (min)
k 10-3 (1/min)

15
30
20 10

10 5

0 0
0 50 100 150 200 250 0 5 10 15 20 25 30
1/I 10-2 (m2/A)
20
40 5.55 mmol/L 5.55 mmol/L
1/k 101 (min)
k 10-3 (1/min)

15
30
10
20
10 5

0 0
0 50 100 150 200 250 0 5 10 15 20 25 30
I (A/m2) 1/I 10-2 (m2/A)

Fig. 3. Experimental rate constant k of electrochemical calcite precipitation as a function of current density I (A/m2) for the five different Ca2+ concentrations of the solutions.

10 Scalcite (Eq. (5)) is not the sole factor controlling electrochemical calcite
precipitation.
The electrochemical calcite precipitation in a 3.33 mmol/L Ca
8
(HCO3)2 solution was evaluated per hour for a current density of
mCa 102(min A/m2)

100 A/m2. According to Eq. (14) the experimental rate constant k

6 could be calculated to 35.2 10− 3 (1/min). By substituting k in Eq. (13),
the removed Ca2+ concentration per hour for the experimental
electrode area of 25 cm 2 was calculated to be 2.93 mmol/L.
4
This corresponds to a precipitated mass of 117 g CaCO3/h m2. This
value is approximately comparable with the result of Hasson et al.
2 [10], who measured a maximum precipitation rate of about 100 g
CaCO3/h m2.
0
1 2 3 4 5 6 3.3. Electrochemical Mg2+ removal
Ca2+ (mmol/L)
Fig. 5 shows the experimental rate constant k or the electrochem-
Fig. 4. Calculated slopes mCa for the five Ca2+ concentrations of the solutions. ical precipitation rate of brucite as a function of the current density
 Author's personal copy

K. Zeppenfeld / Desalination 277 (2011) 99–105 103

80 1.72 mmol/L 80 1.72 mmol/L

k 10-3 (1/min)

k 10-3 (1/min)
60 60

40 40

20 20

0 0
0 50 100 150 200 250 0 10 20 30 40 50 60

80 2.30 mmol/L 80 2.30 mmol/L

k 10-3 (1/min)
k 10-3 (1/min)

60 60

40 40

20 20

0 0
0 50 100 150 200 250 0 10 20 30 40 50 60

80 3.45 mmol/L 80 3.45 mmol/L

k 10-3 (1/min)

k 10-3 (1/min)
60 60

40 40

20 20

0 0
0 50 100 150 200 250 0 10 20 30 40 50 60

80 4.60 mmol/L 80 4.60 mmol/L

k 10-3 (1/min)

k 10-3 (1/min)

60 60
40 40

20 20

0 0
0 50 100 150 200 250 0 10 20 30 40 50 60

80 5.75 mmol/L 80 5.75 mmol/L

k 10-3 (1/min)
k 10-3 (1/min)

60 60
40 40
20 20

0 0
0 50 100 150 200 250 0 10 20 30 40 50 60
I (A/m2) I2 103 (A2/m4)

Fig. 5. Experimental rate constant k of electrochemical brucite precipitation as a function of current density I (A/m2) for the five different Mg2+ concentrations of the solutions.

I (A/m2) for the five different Mg2+ concentrations listed in Table 1. 10

With increasing I and thereby increasing OH− quantities the rate
constant shows a strong augmentation. This effect is more pronounced
8
mMg 10-6 (m4 /min A2)

at smaller Mg2+ concentrations. As k is plotted as a function of I2

(A2/m4), the dependence becomes linear (Fig. 5) and corresponds to
following equation 6

2
k = mMg I ð15Þ
4
where mMg is the slope of the straight lines. A plot of mMg, calculated
by linear regression at the five different Mg2+ concentrations is 2
shown in Fig. 6. It is demonstrated that the slopes decrease with
increasing Mg2+ concentration. Therefore, the above described
0
augmentation of electrochemical brucite precipitation decreases 1 2 3 4 5 6
with increasing Mg2+ concentration. Mg2+ (mmol/L)
In aqueous solutions the growth rate r of brucite as well as of
calcite, follows an expression of the form of r ~ (Sbrucite − 1)x, whereby Fig. 6. Calculated slopes mMg for the five Mg2+ concentrations of the solutions.
 Author's personal copy

104 K. Zeppenfeld / Desalination 277 (2011) 99–105

r corresponds to a linear (x = 1) [23] or parabolic dependence (x = 2) 15

[16] on the degree of supersaturation Sbrucite. The electrochemical 0.3 mS/cm

E 10-4 (kWh/mmol CaCO3)

precipitation rate k increases with the square of the current density I2 12 0.4 ms/cm
(Fig. 5) and consequently with the square of the OH− concentration. 0.6 ms/cm
Therefore it can be concluded that the Mg2+ ions of the solution bulk
0.8 mS/cm
directly react with OH− ions without any diffusion limitations in the 9
1.0 mS/cm
mass transfer. Thus the electrochemical precipitation rate k increases
with increasing supersaturation Sbrucite as the square of the OH−
6
concentration in the reaction zone determined the degree of Sbrucite
(Eq. (7)).
The observation that the augmentation of brucite precipitation 3
decreases with increasing Mg2+ concentration (Fig. 6) has also been
observed by Liu and Nancollas [24]. They demonstrated that aqueous
mixtures of MgCl2 and NaOH, containing excess Mg2+ ions showed a 0
0 4 8 12 16 20
smaller crystallization rate than those with excess OH− ions. Morpho-
U (V)
logical observations indicate a change in the particle morphology,
average diameter, diameter to thickness ratio and surface area of brucite Fig. 7. Energy consumption E (kWh) required for 1 mmol CaCO3 precipitated as a
crystals at high pH values (pH N 11) or high OH− concentrations [25]. function of the applied voltage U (V) for the different electric conductivities κ25 of the
From the results it can be concluded that a small concentration solutions.
ratio (Mg2+)/(OH−) or a high pH value promote the concentration
+
of MgOH(aq.) species in the solution, which are responsible for catalysing with the square of the electric current I2z . Therefore the time t to
+
brucite precipitation [16]. Therefore the high pH and the high MgOH(aq.) precipitate 1 mmol Mg(OH)2 is considerably shorter at high electric
concentration in the negative reaction zone (cathode) result in an currents (Eq. 13). Thus energy consumption E is nearly independent
enhanced precipitation rate as demonstrated by Fig. 5 and Fig. 6. of the applied voltage and only increases with decreasing solution
The electrochemical brucite precipitation in a 3.45 mmol/L Mg conductivity (Eq. (16)).
(HCO3)2 solution was evaluated per hour for a current density of
100 A/m2 as follows. According to Eq. (15) with a value of mMg = 3.1 4. Conclusions
10− 6 (m4/A2min) the experimental rate constant k can be calculated
to be 31.0 10− 3 (1/min). Substituting k in Eq. (13), the removed Mg2+ The present study demonstrates that calcite and brucite precipi-
concentration per hour for the experimental electrode area of 25 cm2 tation occurs through a chemical process following the electrochem-
is calculated to be 2.91 mmol/L. This corresponds to a precipitated ical generation of OH− ions in the vicinity of the electrode surface. The
mass of 68 g Mg(OH)2/h m2. electric current density initially augments the electrochemical
precipitation of calcite, but a sufficiently high current density the
3.4. Energy consumption precipitation rate reaches a limit. Furthermore, the precipitation rate
of calcite does not vary with the Ca2+ concentration. The results
An additional major parameter influencing the economics of the suggest that limitations in the mass transfer of HCO− 3 ions from the
electrochemical precipitation processes is the specific energy con- solution bulk towards the very vicinity of the cathode are responsible
sumption. A great part of the applied voltage is consumed by the for the limitation in precipitation rate. In contrast, the electrochemical
ohmic drop in the bulk solution and inside the porous crust of the precipitation of brucite shows a strong augmentation with increasing
cathode. The solution resistance depends on the solution conductivity current density. There are no limitations in the mass transfer, as the
κ25 and on the distance between the electrodes d which is Mg2+ ions of the solution bulk directly react with the OH− ions
demonstrated by Eq. (11). On the basis of Eq. (13) the duration of produced in the vicinity of the cathode. With increasing Mg2+
+
the electrolysis t required to precipitate 1 mmol CaCO3 or Mg(OH)2 concentration the rate constant decreased, as MgOH(aq.) species are
ions can be calculated. Therefore the energy consumption E (kWh) for responsible for catalyzing brucite precipitation. A high pH value or a
an electrochemical precipitation of 1 mmol CaCO3 or Mg(OH)2 can be small concentration ratio (Mg2+)/(OH−) promote the concentrations
+
evaluated as follows [26]: of MgOH(aq.) species in the reaction zone. Furthermore, the specific
  
1 d 2 15
E = ð1:23Iz Þ + I t ð16Þ
κ25 A z 0.3 mS/cm
E 10-4 (kWh/mmol Mg(OH)2)

12 0.4 mS/cm
where (1.23 Iz) is the electrochemical energy consumption and (1/κ25
0.6 mS/cm
d/A) I2z is the energy consumption which was transformed in Joules
heat. Iz is the electric current measured at the beginning of the 0.8 mS/cm
9
electrolysis. 1.0 mS/cm
Fig. 7 shows the specific energy consumption E required for
1 mmol CaCO3 precipitated as a function of the applied voltage U (V) 6
for the five different solution conductivities κ25. With higher applied
voltage and consequently higher electric current Iz the precipitation of 3
calcite runs comparatively slower (Fig. 3 and Eq. (13)) than with
lower electric current but the amount of energy required is
considerably greater. This effect is more pronounced at smaller 0
solution conductivities as demonstrated by Eq. (16). 0 4 8 12 16 20
The specific energy consumption E required for 1 mmol Mg (OH)2 U (V)
precipitated as a function of the applied voltage U (V) for the five
Fig. 8. Energy consumption E (kWh) required for 1 mmol Mg(OH)2 precipitated as a
different solution conductivities κ25 is shown in Fig. 8. It is function of the applied voltage U (V) for the different electric conductivities κ25 of the
demonstrated by Fig. 5 that the rate of brucite precipitation increases solutions.
 Author's personal copy
K. Zeppenfeld / Desalination 277 (2011) 99–105
energy consumption to remove 1 mmol/L Ca2+ ions increases
strongly with the applied voltage as higher voltages promote the
transformation in Joules heat. In contrast, the specific energy
consumption for 1 mmol/L Mg2+ removal is nearly independent of
the applied voltage.
This study allows a better understanding of the electrochemical
precipitation processes as the effect of operational parameters such as
applied voltages, current density and content of scale forming ions
were investigated. Furthermore, the electrochemical technology for
scale prevention holds promise to find cost benefit applications in
various industrial processes and in the water supply.
References
[1] Drew Ameroid, Fundamental of industrial water treatment, Vulkan Verlag, Essen,
1997.
[2] Z. Amjad (Ed.), Mineral Scale Formation and Inhibition: Proceedings of an
American Chemical Society Symposium, 1994, Washington, D.C.
[3] A. Bannoud, The electrochemical way of removing the hardness of water,
Desalination 93 (1993) 545–555.
[4] K. Zeppenfeld, Electrolysis as a method for partial decarbonisation, GWF Wasser
Abwasser 139 (1998) 86–91.
[5] K. Zeppenfeld, Removal of carbonate encrustation by electrolysis of calcareous
solutions, Chem. Ing. Technol. 21 (1999) 583–587.
[6] K. Zeppenfeld, Electrochemical water softening as alternative to cation
exchangers, Chem. Ing. Tech. 72 (2000) 101–106.
[7] C. Gabrielli, G. Maurin, H. Francy-Chausson, P. Terry, T.T.M. Tran, M. Tlili,
Electrochemical water softening: principle and application, Desalination 201
(2006) 150–163.
[8] D. Hasson, V. Lumelsky, G. Greenberg, Y. Pinhas, R. Semiat, Development of the
electrochemical scale removal technique for desalination applications, Desalina-
tion 230 (2008) 329–342.
[9] K. Raman, J.J. Lenhart, Electrolytic magnesium recovery from drinking water
membrane residuals, J. Appl. Electrochem. 39 (2009) 1683–1693.
[10] D. Hasson, G. Sidorenko, R. Semiat, Calcium carbonate hardness removal by a
novel electrochemical seeds system, Desalination 263 (2010) 285–289.
View publication stats
105
[11] Landolt Börnstein, in: J. Bartels, P. Ten Bruggencate, H. Hausen, H. Hellwege, K.H.
Schäfer, E. Schmidt (Eds.), Numerical Values and Functions, II, Springer, Berlin
Göttingen Heidelberg, 1960, Part 7.
[12] L. Onsager, R.M. Fuoss, Irreversible processes in electrolytes. Diffusion, conduc-
tance and viscous flow in arbitrary mixtures of strong electrolytes, J. Phys. Chem.
36 (1932) 2689–2778.
[13] W.A. House, Kinetics of crystallization of calcite from bicarbonate solutions, J. Chem.
Soc. Faraday Trans. 77 (1981) 341–359.
[14] Y. Lin, P.C. Singer, Effects of seed material and solution composition on calcite
precipitation, Geochim. Cosmochim. Acta 69 (2005) 4495–4504.
[15] K. Zeppenfeld, Calcite precipitation from aqueous solutions with different calcium
and hydrogen carbonate concentrations, J. Water SRT-Aqua 59 (2010) 482–491.
[16] O.S. Pokrovsky, J. Schott, Experimental study of brucite dissolution and
precipitation in aqueous solution: Surface speciation and chemical affinity
control, Geochim. Cosmochim. Acta 68 (2004) 31–45.
[17] M.M. Reddy, G.H. Nancollas, The crystallization of calcium carbonate: isotopic
exchange and kinetics, J. Colloid Interface Sci. 36 (1971) 166–172.
[18] H.J. Meyer, Growth rate of calcite in aqueous solution, J. Cryst. Growth 47 (1979)
21–28.
[19] A. Gutjahr, H. Dabringhaus, R. Lacmann, Studies of the growth and dissolution
kinetics of the CaCO3 polymorphs calcite and aragonite. I Growth and dissolution
rates in water, J. Cryst. Growth 158 (1996) 296–309.
[20] T.F. Kazmierczak, M.B. Tomson, G.H. Nancollas, Crystal growth of calcium
carbonate, a controlled composition kinetic study, J. Phys. Chem. 86 (1982)
103–107.
[21] A.E. Nielsen, M.B. Toft, Electrolyte crystal growth kinetics, J. Cryst. Growth 67
(1984) 278–288.
[22] M.G. Lioliou, C.A. Paraskeva, P.G. Koutsoukos, A.C. Payatakes, Heteregeneous
nucleation and growth of calcium carbonate on calcite and quartz, J. Colloid
Interface Sci. 308 (2007) 421–428.
[23] C. Chieng, G.H. Nancollas, The crystallization of magnesium hydroxide. A constant
composition study, Desalination 42 (1982) 209–219.
[24] S.T. Liu, G.H. Nancollas, The crystallization of magnesium hydroxide, Desalination
12 (1973) 75–84.
[25] V.A. Phillips, J.L. Kolbe, H. Oppenhauser, Effect of pH on the growth of Mg(OH)2
crystals in an aqueous environment at 60 °C, J. Cryst. Growth 41 (1977) 228–234.
[26] Ullmanns Encyclopaedia of Chemical Engineering, 3, Verlag Chemie, Weinheim,
1972, Part 2.