Controlling Scales Issues in Hard Water

Distribution
Noor Syazwani binti Azmi
Chemical Engineering Department
Universiti Teknologi PETRONAS
Seri Iskandar, 32610 Perak, Malaysia
noorsyazwaniazmi2@gmail.com

Abstract This research investigate scales issue in hard water 2HCO3- + heat CO3= + CO2 (gas) + H2O (1)
issues in pipeline system. Basically the purpose of this project is The carbornate then reacts with calcium
to reduce the scale formation in hard water flow using magnetic
field influence. Scaling always give a big issue in industry Ca++ + CO3= CaCO3 (solid) (2)
especially in the condition of hard water medium mostly found in Ca++ + 2HCO3- CaCO3 (solid) + CO2 (gas) + H2O (3)
the fertilizer application. Calcium carbonate scaling in the
pipeline was induced using carbon dioxide bubble and the scale Anti-scale magnetic treatment for hard water flow has a
was formed after expected period of observation. Neodymium long controversial history, [2]. The phenomenon of water
magnet was installed to influence the water in reducing the
treatment with an applied magnetic field has been known for
scaling and observation was made to see the different after
passing through magnetic field. To gain the details insight on the many years and has been reported as being effective in
precipitation produced, the sample will be characterized by SEM numerous instances and has been established that the
and XRD for the phase identification of precipitation formed. crystallisation of calcium carbonate, CaCO3 in hard water can
The previous result found on some article shown that there were be influenced by the magnetic field. Strong neodymium
changes on the crystalline characteristics of the precipitation magnets, the most widely used rare earth magnet are often used
between the hard water that undergo magnetic treatment and the in magnetic water treatment to prevent or reduce scale
non-treated hard water. For this experiment, it shows the positive formation in hard water distribution [3]. The magnetic field
result where the amount of calcium carbonate was decrease in the effect the molecules of the hard water, the ion of the calcium
magnetic water treatment by using different pole of magnet. The carbonate that can reduce the scaling formation after the hard
XRD result shown the amount of the calcite in the magnetic
treated water also decrease by 36.61% and the SEM result shown
water flow through the magnetic bar. The different polarity of
different crystalline characteristics of the calcium carbonate of the magnet give different result in terms of the scaling
hard water and the magnetic treated water. formation. Magnetic water treatment does not remove any
calcium from the water [4]. This work investigate the effect of
I. INTRODUCTION magnetic field on scaling prevention by using neodymium
magnet, to determine the magnetic polarity effect on scaling
The scaling problem in hard water arises because of the development and to characterize the carbonate crystallization
solubility of calcium carbonate, CaCO3 decreases with minerals in the pipeline if any deposits still exist. However, the
increasing temperature, [1]. Huge amount of energy and cost anti-scale magnetic treatment has had a long and controversial
wasted because hard scale forms in the equipment in plant such history in example, either effective or ineffective operating
as heat exchanger, boilers and domestic hot water system can have been reported [5]. However, conflicting results also exists
lead to many problems such as corrosion, pipe blocking and in the literature. For example, the magnetic field would supress
economics impacts to the industry and waste water treatment. [6][7][8][9], or have no effect [10][11] on the CaCO3 growth,
CaCO3 crystallises in three different crystals forms that are hence creating a widespread controversy as to the credibility of
calcite, aragonite and vaterite. Calcite is usually associated this type of water conditioning, such as the conclusion of [12]
with a hard scale whereas aragonite and vaterite give rise to a that the effectiveness of a magnetic water treatment device was
softer type of scale that is easily removed. attributed to the contamination of solution by Fe ions, which
dissolved from the device and inhibited the build-up of scale.
Scaling is a phenomenon occurs when the water contain
calcium and magnesium and also known as hard water react We can analyzed the effect of magnetic field on the CaCO 3
and form precipitation. It can occur when the concentration of precipitation crystals formed using x-ray diffraction analysis
calcium or magnesium ion (salt) is higher in the water. The [13]. The aragonite form of precipitation found in the
presence of heat also contribute to the formation of scales. The precipitation more than the formation of calcite when using
scale will be formed when calcium ion react with bicarbonate magnetic field. Many studies were published on the effect of
ion when heating. The equations 1 to 3 show how scaling is magnetic field on the crystallization of CaCO 3 [14][15]. He
formed: concluded that the hard scaling that is calcite can be prevent
successfully using magnetic field.
 I. METHODOLOGY D. Characterization of CaCO3 using XRD
The X-ray powder diffraction was used for phase
A. Preparation Hard Water identification in the precipitation of the calcium carbonate.
Sample solutions of calcium hydroxide Ca(OH)2 were Data were collected in the 2 angle mode from 20 to 70 o in
prepared by dissolving finely ground calcium hydroxide steps of 0.04o; the integration time was 30 s per step. The
powder of analytical purity in deionised water and then let the divergence and anti-scatter slits were fixed within 10 and the
solution to fully dissolve overnight. This solution provide the front slit was 0.2 mm wide.
hard water with the pH of 12.

E. Characterization of CaCO3 using SEM

B. Non-treated Water The scanning electron microscope (SEM) was used for the
The experiment of the non-treated water was done for the study of the nucleation and the form of the crystals. The
sake of comparison with the magnetically treated water. The analytical electron microscopy was used and the samples for
hard water was flow in the water system at room temperature the SEM observation and analysis used HV of 10 000kV,
with pH of 12 and bubbling the suspension with carbon- magnificent of 2000x and working distance of 10.5 mm. The
dioxide gas through a porous frit. As CO 2 is bubbled in the micro-sized particles were collected and examined under the
solution, the solution become cloudy and let the solution electron microscope.
stable and for some expected time. Then, CaCO 3 particles
begin to precipitate. II. RESULTS AND DISCUSSION

C. Magnetic Water Treatment

A. Non-treated Water
For the magnetic water treatment, the same method was
using in preparation of hard water by using the calcium
hydroxide. After the solution was ready, the hard water undergo At the first stage, the experiment was done by not using
the water system that installed with neodymium so that the any magnetic. This is for the sake of comparison with the
solution will pass through the magnetic field for certain time in experiment that using magnetic field. From this experiment,
the circulation water system. After that, the solution was the precipitation of CaCO3 amount is quite high compared to
bubbled with CO2 gas to induce the precipitation of CaCO 3. the magnetic water treatment that is 0.173 g average of three
The water system and the description of the magnetic water run shown in the table 4.1. Figure 4.1 below showed the
treatment are shown in the figure 3.2 and figure 3.3 above. amount of the CaCO3 produced from non-treated water.
The CaCO3 precipitation was filtered out and dried in the
oven with 110oC for 3 hours to get the CaCO 3 samples
powders. The first experiment was not undergo the magnetic
field for the sake of comparison. Then, the experiment of the
treated hard water was repeated using different number of
neodymium magnet and also the variations of the pole of the
magnet.
The experiment is repeated using the different numbers of
magnets pairs and different arrangement of the magnetic pole.
The CaCO3 solid formed from the experiment was collected for
the further analysis.

Fig. 2: Graph of a mount of CaCO3 precipitation from non-

treated water

In order to get this amount of precipitation, the experiment

was done for three days and the result was collected per day
basis. From fig. 3 below, the scaling rate is decrease by day
from day one to day three of the experiment. This is because,
the concentration of the solution decrease by day.
Fig 1: a) Sketch of setup for magnetic treatment of circulating
water and b) permanent magnets disposition
 through the magnetic field for 10 minutes and 10 minutes of
CO2 bubbling through the system. The amount of precipitation
is tabulated in the graph below.

Fig 3: The scaling rate of the accumulation of precipitation

Run 1.
Fig. 5: Graph of amount CaCO 3 precipitation using magnetic
field (different pole)
B. Effect of Temperature on Precipitation
From graph in Fig. 5, the amount of precipitation increase
The scaling problem in hard water arises because of the with the increasing the number of magnets. The percentage of
solubility of calcium carbonate, CaCO3 decreases with reduction also decrease when increasing the number of
increasing temperature, [1]. The Fig. 4 below shown the magnet.
difference of the amount precipitation collected by using
different temperature. The precipitation of the calcium As predicted, the amount of precipitation in the magnetic
carbonate increasing when increasing the temperature but kept water treatment with different pole (attraction force) will be
constant after 455C and it is the optimum temperature of the increasing when increase the amount of magnet. When we
maximum precipitation of calcium carbonate with the range increase the amount of magnet, the strength of magnet also
about 0.330g/L. increase and the attraction force become strong. The attraction
force attract the positive and negative ion in the hard water
and as the result, the ions were collide each other because of
the strong attraction force. When they collide each other, they
tend to stick together and form the precipitation.

D. Magnetic Water Treatment (same pole of magnet

repulsion)

The same neodymium magnet with strength of 1400mT

were used with different number of magnet for five run but
using the same pole of magnets that is repulsion force. First
we used a pair of magnet then increase the number of magnet
by two for five run. For every run, the hard water was passed
Fig. 4: The precipitation product at different temperature through the magnetic field for 10 minutes and 10 minutes of
CaCO3 CO2 bubbling through the system. The amount of precipitation
is tabulated in the Fig. 6 below. From the graph below, the
The pH of the solution is originally pH of the lime water amount of precipitation decrease with the increasing the
that is 12.1 and the flowrate of the water was keep constant number of magnets and the percentage of reduction also
throughout the experiment that is 0.8 dm3/min. increase when increasing the number of magnet.

C. Magnetic Water Treatment (different poles of magnet The using of magnetic field with repulsion force (same
attraction) pole) does give the best result for this experiment. The
magnetic field force the positive and negative ions to repel
each other. The ions do not have the opportunity to collide
The neodymium magnet with strength of 1400 mT were each other and resulting in less formation of precipitate than
used with different number of magnet for five run using the attraction force by using different pole of magnet.
different pole of magnets means using attraction force. First
we used a pair of magnet then increase the number of magnet
by two for five run. For every run, the hard water was passed
 aragonite forms of crystals when there is the magnetic force. It
can be easily remove from the pipeline since it is not stick to
each other and really hard to stick to the pipeline.

F. XRD Result

The x-ray diffraction was used for the phase identification

of CaCO3 in the non-treated water and also in the
magnetically treated water. Graph from Fig. 8(a) below shows
the diffractogram xrd result of the calcium carbonate CaCO3
crystal for non-treated water. Meanwhile the Fig. 8(b) shows
Fig 6: Graph of amount CaCO3 precipitation using magnetic
the diffractogram xrd result for the magnetically treated water.
field (same pole)
The analyses result shows in the Fig. 8 (a) and Fig. 8(b)
E. SEM Result was summarize in the Table 1 below. The percentage of
CaCO3 (calcite) in the magnetically treated water is lower
The morphology of the calcium carbonate CaCO 3 crystals than in non-treated water by matching with pure standard of
obtained was checked using Scanning Electron Microscope CaCO3 (calcite). The percentage of calcite in magnetically
(SEM). The result from SEM both for non-treated water and treated water is only about 38.27% compared to non-treated
also the magnetic treatment water were shown below. As water and the pure standard of CaCO3 (calcite) that are
expected both conditions will give different crystal surface 43.16% and 74.88% respectively.
morphology even from the same product that is calcium
carbonate.

Fig 7: a) Photomicrograph result for non-treated water,

b) Photomicrograph result for magnetic treatment water

From Fig. 7(a), the morphology of the crystals looks like

rhombohedral and tubular form. This morphology usually was
the calcite form of crystals. As explained earlier, calcium
carbonate crystalizes in three different forms that is calcite,
aragonite and vaterite. Calcite is one type of crystals that can
form hard scale and really hard to remove. So from the
photomicrograph of SEM above, the non-treated water
produce the calcite crystal of calcium carbonate. The
rhombohedral form of crystals stick to each other even in the Fig. 8: a) Diffractogram xrd for non-treateted water
small form of crystals. This will make the crystals really hard b) Diffractogram xrd for magnetically treateted water
to remove or to make it separate from stick to each other and
this is the characteristics of a calcite.
Table 1: Percentage of Calcite
Fig. 7(b) shows the precipitate is made of partially calcite Source of CaCO3 Calcite (%)
transformed into aragonite fibrous form of crystals because of Pure CaCO3 74.88
the effect of magnetic force on the crystallization structure. CaCO3 from non-treated water 43.16
This type of crystals also known as flos-ferri flowers of iron. CaCO3 from magnetically
38.27
There are also partially calcite in the magnetically treated treated water
water crystals but in bigger size and not stick to each other
with another calcite crystals. This big calcite will transform to
 III. CONCLUSION AND RECOMMENDATIONS Dynamic Fluid Systems., Regional Symposium On Chemical
Engineering , Indonesia
As a conclusion, this project is essential as it suggests a [3] Ambashta, R. D. and M. Sillanp (2010). "Water purification using
ways of reducing the scaling in hard water pipeline based on magnetic assistance: A review." Journal of Hazardous Materials 180(1
the calcium hydroxide, CaOH solution (lime water). It was 3): 38-49.
found that the magnetic field can change the crystallization [4] Fathi, A., et al. (2006). "Effect of a magnetic water treatment on
homogeneous and heterogeneous precipitation of calcium carbonate."
product of calcium carbonate in the hard water medium. From Water Resources 40(10): 1941-1950.
this study also, the magnetic water treatment using same [5] Duffy, E. A. 1977. Investigation of Magnetic Water Treatment Devices.
magnet polarity with repulsion force give the best result of Ph.D. dissertation, Clemson University, Clemson, S.C.
calcium carbonate scaling prevention. For the different pole of [6] Kobe, S., et al. (2002). "Nucleation and crystallization of CaCO3 in
magnet used, the percentage of reduction is about 84.4% applied magnetic fields." Crystal Engineering 5(3-4): 243-253.
reduction from the non-treated water. [7] S.Kobe, G. Drazic, P.J.McGuiness, J.Strazisar. (2001). Journal of
Magnetism and Magnetic Materials: Magnetic Water Treatment 236, 71-
76.
There are a few recommendations that I would suggest to
[8] Tai, C. Y., et al. (2008). "Effects of magnetic field on the crystallization
overcome the difficulties and limitations throughout this of CaCO3 using permanent magnets." Chemical Engineering Science
project. First, this magnetic water treatment also provide 63(23): 5606-5612.
descaling in the pipeline but these may take up months of [9] Barrett, R.A., Parsons, S.A., 1998. The influence of magnetic fields
process with the complete water system and proper magnetic on calcium carbonate precipitation. Water Res. 32 (3), 609612.
water treatment system also. Further study is needed to study [10] Ali, Y., et al. (2014). "Magnetic Water Treatment in Environmental
about the descaling process. Next, this scaling prevention also Management: A Review of the Recent Advances and Future
Perspectives." Current World Environment 9(3): 1008-1016.
can be studied by using magnesium and iron compound from
[11] Hasson, D., and D. Bramson. 1985. Effectiveness of magnetic water
synthetic water or real water source. treatment in suppressing CaCO3 scale deposition. Ind. Eng. Chem.
Process Des. Dev. 24: 588-592
[12] Herzog, R.E., Q. Shi, J.N. Patil & J.L. Katz. 1989. Magnetic water
treatment: The effect of iron on calcium carbonate nucleation and
ACKNOWLEDGMENT growth. Langmuir, 5: 861-867.
I would like to thanks Universiti Teknologi Petronas [13] A.C. Cefalas, Kobe, S. Draic, G. Sarantopoulou, E. Kollia, Z. Straiar,
J. Meden, A. (2008). Nacocrystalization of CaCO3 at solid /liquid
for the facilities and equipment provided for me throughout the interfaces in magnetic field: Quantum approach. Applied Surface
experiment and also special thanks to my supervisor, family Science 254; 6715-6724
and colleagues. [14] Dalas, Evangelos, and Petros G. Koutsoukos, The Effect of Magnetic
Fields on Calcium Carbonate Scale Formation, Journal of Crystal
Growth, 1989, Vol. 96, No. 4, pp. 802-806.
REFERENCES [15] Parsons, S. A., S. J. Judd, T. Stephenson, S. Udol, and B.-L. Wang. 1997.
Magnetically augmented water treatment. Process Safety and
[1] Strum W., and Morgan J. P, 1940, Aquatic Chemistry, Wiley, New Environmental Protection. Transactions of the Institution of Chemical
York. Engineers 75 (Part B): 98-104.
[2] Nelson, S., Achmad, F., Bismo, S., & Roekmijati, W. S. (2007). Effects
Of Magnetic Field On Calcium Carbonate Precipitation In Static And