MATEC Web of Conferences 58, 01029 (2016) DOI: 10.

1051/ matecconf/20165801029
BISSTECH 2015

CALCIUM CARBONATE SCALE FORMATION IN COPPER PIPES ON

LAMINAR FLOW
Raharjo, S*, Bayuseno, Ab, Jamarib, Muryanto, Sc
*Department of Mechanical Engineering, Muhammadiyah University in Semarang, Indonesia
bDepartement of Mechanical Engineering, Diponegoro University, Semarang Indonesia
cDepartment of Chemical Engineering, UNTAG University in Semarang, Semarang Indonesia
*Corresponding author. Tel. +62-8164242537, +62-8445768
E-mail address: *samraharjo2@gmail.com; apbayuseno@gmail.com

ABSTRACT
Calcium carbonate is commonly precipitated as a scale in the transportation pipes of water. The presence of this mineral
deposit becomes problematic, because it can block the pipes and lead to a decline in piping performance. Calcium
carbonate precipitation from the synthetic solution was experimentally investigated in the present study. The aim of
research was to predict the occurrence of precipitates and characterize the scale precipitated from the solutions. The
synthetic solutions were prepared using CaCl2 and Na2CO3, which was mixed with distilled water (H2O). The
concentrations of Ca2+ at 2000, 3000, 4000 and 5000 ppm. in the solution were adjusted and the solution flow in the Cu
pipes at the different flow rate of 30, 40 and 50 ml/min. It was found that in all the experiments, the conductivity decreased
abruptly after a certain induction period. Higher temperature produced more mass of the scale indicating that the increasing
temperature promote scale formation. SEM analysis showed that the scale was rhombohedral, while EDS revealed that the
elemental composition of the scale consisted of Ca, C and O. The crystalinity of the scale was found to be mostly calcit as
shown by the XRD

Keywords: calcium carbonate, induction time, prototipe scale formation, scale morfology

INTRODUCTION
Scaling is one of the main serious engineering to scale growth and agglomeration (Rabizadeh et al.,
problems in process industries as the scales my hinder 2014). This is due to the random collision of ions with
the flow of solution in industrial pipes or tubes. Accurate particles and secondary crystallization occurs on the
estimation of scale formation is thus very important. surface of these foreign bodies present in the bulk phase
Calcium sulphate, carbonate potentionaly deposited add (Alice et al., 2011).
clogged pipping system (Azimi and Papangelakis, 2010). In electrolyte solutions, the transition temperature
The calcium carbonate scale formation was of calcium carbonate solubility may vary because of
influenced by several aspects such as flow rate, variation in the water activity (Fathi et al., 2006). The
concentration of solution, pH value, temperature, solubility of common scales in water is shown in Figure
pressures, and ionic strength (Bahadori, 2010). In 1, solubility of CaCO3, BaSO4 and CaSO4 as a function
laminar turbulence,the higher flow rates,the more of temperature.
calcium carbonate scale mass indicating the fluid flow
enchances the scale formation (Muryanto et al., 2012).
Previous studies done by Gourdon, have shown that
CaCO3 scale formation can be found in fully laminar and
fully turbulent. In fully laminar the formation was in a
slow growth while in fully turbulent the formation was
easily found in the angels (Amor et al., 2004). The flow
of the fouling is described as having pronounced rippling
and surface waves of partially laminar and partially
turbulent nature.As the turbulent also will enhance the
mass transfer,the rate of crystal deposition can also be
promoted (Gourdon, 2011).
Other researchers indicated that scale growth does
not always remain linear with time,as higher velocity can
sometimes reduce scale deposition (Basim et al., 2012).
Crystallization occurs due to the lateral growth of the Figure-1. Solubility of Common Scalesas a function of
scale deposit on the membrane surface, resulting in flux temperature (Amer, 2009).
decline and surface blockage (Zhang, 2002). Thus,the The aim of the present research was to examine the
scaling formation is actually the crystallization nucleation and growth of calcium carbonate crystals, and
phenomenon.Bulk crystallization arises when crystal identify calcium carbonate formation and the scaling
particles are formed in the bulk phase through potential in pipes. In the present study, calcium sulfate
homogeneus crystallization and my deposit on crystals were grown by the prepared solution containing
membrane surfaces as sediments/particles to form a cake calcium carbonate composition and then characterized
layer that leads to flux decline (Zhen et al., 2010). In by XRD for the mineral determination and SEM analysis
addition, supersaturated scale forming conditions leads with EDX for elemental analysis and morphology.
© The Authors, published by EDP Sciences. This is an open access article distributed under the terms of the Creative Commons Attribution
License 4.0 (http://creativecommons.org/licenses/by/4.0/).
MATEC Web of Conferences 58, 01029 (2016) DOI: 10.1051/ matecconf/20165801029
BISSTECH 2015

METHODOLOGY Experiments using a scaling simulator are shown in

Materials and Apparatus Figure 2.
All solutions used in this study were prepared Further, induction time of precipitation was
by dissolving reagent grade chemicals directly without measured by a conductivity method. This method was
further purification. The solution was prepared under employed in the present study to measure the induction
saturated calcium sulfate by mixing directly into glass time for nucleation of calcium sulfate precipitation. The
containers two equimolar solutions of calcium chloride conductometer with a Consort C831 analyzer was used
dihydrate (CaCl2•2H2O, minimum assay 99%, Sigma) for each experiment at specified condition of the
and anhydrous sodium carbonate (Na2CO3, analytical repeated three times. Therefore, the induction times and
grade, Sigma). Both reactants were dissolved in aqueous precipitation results presented in this study are the
solutions containing 10 L of water and the solution average of three values. In order to minimize costs of
concentration of Ca2+ was adjusted to be 2000, 3000, EDX analysis, the three samples were mixed and
4000 and 5000 ppm respectively. The selected range of analyzed for crystal shape, crystal structure, and density.
temperatures was 30 to 40 °C. Each solution was then Each stock solution was then filtered through 0.22 μm
poured into a tube made of stainless and stirred at low paper filters to eliminate the presence of impurities, and
speed. Two of the tube is connected with two brands of stored at room temperature before subsequently analyzed
Iwaki magnetic pump long and trial test was conducted by SEM/EDX.
for 8 hours for each treatment with different flow rates.

Figure-2: Experimental setup used in the CaCO3 precipitation

Materials Characterization reduction of the solute concentration in the solution at

The characterization of the precipitating scales was the detectable extent through conductometry.
conducted through scanning electron microscopy In the present study, the reaction was continued for
coupled with energy dispersive X-ray analysis (SEM- about 25 minutes after the induction time until the nuclei
EDX). SEM apparatus equipped with an EDX was used were formed into the coupon and observed in computer
for characterizing the microstructure and morphology. monitors. Figure 3 shows the changes in conductivity
For the observation, the powder crystals were mounted during the course of nucleation experiment at room
on a circular metallic precipitate holder and finally temperature and flow rates of 30, 40, and 50 ml/min.
sputtered with gold.

RESULTS
Induction Time of crystallization
Induction time can be defined as the time required
for between the generation of supersaturation and
appearance of nucleic detected through concentration
change. This can be seen since the onset of nucleation
showing a reduction in the concentrations of
crystallizing ion and molecules take place due to their
association into the solid phase, thus the conductivity
which is proportional to the concentration will undergo a
reduction. This reduction in conductivity could be
measured as the induction time. However, the measured Figure-3 Variations of conductivity during the course of
induction time presents the sum of the nucleation time precipitation
for appearance of critical size nuclei. Additionally, Experimental results showed that the induction
growth time of nucleic from critical size to the size time was essentially under the influence of carbonate
possessing enough mass at solid phases makes a concentration. As Figure 3 shows, the induction time

2
MATEC Web of Conferences 58, 01029 (2016) DOI: 10.1051/ matecconf/20165801029
BISSTECH 2015

decreased as the pH solution decreased from 9 to 6.5. (b)

This effect was assumed to be due to an increase in
supersaturation through an increase in hydrogen
concentration. However, pH of the solution was higher
than 9, a longer induction time was observed. The
experimental results of the present study showed that the
induction time for precipitation increased from 20
minutes to 25 minutes. At higher supersaturations, a
lower value of induction time is expected; however, the
temperature will be more influential than supersaturation
due to its order and logarithmic function of effectiveness
(Mullin, 2004).

Flow rates influence on the mass of precipitates

The mass of precipitated calcium sulfate particles
per kg of water at different flow rates and concentration
is presented in Figure-4. As the Ca+2 concentration of
2000 ppm is fixed and the flow rates for the solution Figure-5. Morphology feature is pyramid formed a),
increases in 30 to 50 ml/minutes. An increase in Ca+2 and Compositions chemistry b).
concentration will increase the supersaturation in the
solution due to the removal of free water from the According to theoretical calculations on the
availability of the solute species. This will increase the percentage of weight of CaCO3 Ca content should be
precipitation yield of calcium cabonate. However, the 40%, while the results of the analysis of micro Ca
trend of reduction in precipitation is similar to occur to content = 39.8 % so as to have difference of 0.2 % . For
the different flow rates levels of carbon (C) shall be 12 wt % while result of
analysis of micro C 10.5 % of micro analysis results that
250 have a difference of 1.5% . For oxygen levels should 64
Deposit mass (mg)

%, while the results of the analysis of micro direct 60.06

200
% so as to have difference of 3.94%.From the analysis of
150 SEM-EDX test is concluded, its crust really crystal
CaCO3.
100
50 DISCUSSIONS
The EDX analysis of calcium carbonate as found in
0 this study of precipitates in Cu pipes is probably
25 30 35 40 45 50 55 rhombohidral. It should be considered here that
Velocity (ml/min) precipitates samples to be observed by SEM provides
strong intensities of Ca, O and C elements which is more
2000 ppm 3000 ppm 4000 ppm 5000 ppm frequently found in SEM studies of calcium carbonate.
However, the conditions used for EDX analysis in the
Figure-4. velocity of deposit formed graph present study and the detected amount of impurities
produced a difference in mineral speciation. It is also
Characteristics and morphology of precipitates important the observations of morphologies by SEM in
SEM examination of the CaCO3 scale exhibited a the study of a calcium carbonate with apparent
wide images of calcite and the scales reveal crystalline, rhombohedral habit in the crystal. It can be assumed
there are scales in the structures rhombhohidral is shown from SEM morphology and EDX analysis (Ca, C) to be.
in figure 5. Morphology pyramid formed a) and In contrast, the EDX analysis alone cannot distinguish
Compositions chemistry b). whether the analyzed crystals observed by SEM are
calcit, i.e. calcium carbonate valerite, aragonite and only
(a) by additional XRD techniques could be identified these
minerals. In this case, the precipitation mechanisms of
calcium carbonate mineral phases (calcit, valerite and
aragonite) remain large unexplored. Therefore the role
and implications of valerite as a stable precursor phase to
calcit precipitation observed using XRD method, will
provide interesting results to natural and industrial
processes.

3
MATEC Web of Conferences 58, 01029 (2016) DOI: 10.1051/ matecconf/20165801029
BISSTECH 2015

CONCLUSIONS Cross Flow conditions, Journal. Elsevier aplied Thermal

It was found that in all the experiments, the Engineering. Volume, 36 : 210-218
conductivity decreased abruptly after a certain induction
period. Higher temperature produced more mass of the Fathi, A., Mohamed, T., Claude, G., Maurin, G.,
scale indicating that the increasing temperature promote Mohamed, B. A. 2006. Effect of a magnetic water
scale formation. SEM analysis showed that the scale was treatment on homogeneous and heterogeneous
rhombohedral, while EDS revealed that the elemental precipitation of calcium carbonate. Water
composition of the scale consisted of Ca, C and O. The Research, 40(10):1941-1950.
crystalinity of the scale was found to be mostly calcit as
shown by the XRD. Gourdon. 2011. The Effects of Flow Velocity on
Crystallization Fouling in Falling FilmBlack Liquor
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