SEMICONDUCTORS
THE USE OF HYDRODYNAMIC CAVITATION FOR CALCIUM REMOVAL
FROM ELECTRONICS WASTEWATER
T
he inorganic wastewater
produced in the etching
process for the manufac-
turing of semiconductors
in the electronics indus-
tries contains high con-
centrations of fluoride
and nitrate. The chemical precipitation
process with lime is commonly used to
economically remove fluoride. This
usually results to high calcium residual
in the effluent, which can adversely af-
fect the later stages of wastewater treat-
ment processes, such as membrane biore-
actors (MBR), which are generally in-
corporated for reuse of the wastewater.
Thus, the effective removal of residual
calcium from the effluent of a fluoride
removal process is desirable.
There are many different approaches
to remove dissolved calcium from water
stream. Ion exchange using zeolite and
resin has been proven effective (1, 2).
But this process is not economical for
the large-scale application. Membrane
filtration is also effective, especially with
recent developments in membrane tech-
nologies (3-5). However, membrane
fouling and deterioration often cause
high operation and maintenance costs.
The precipitation method remains as the
most economical method.
In this approach, dissolved calcium is
By Sun-Jip Kim, Ph.D.
Jin-Young Park,
Won-Kwon Lee, Ph.D.,
G&G Co. Ltd.
Wiley Wang, Ph.D.,
VRTX Technologies LLC
Yong-Woo Lee, Ph.D.,
Samsung Engineering Co.
Kyu-Won Hwang
Samsung Electronics Co.
ISSN:0747-8291. COPYRIGHT (C) Tall Oaks
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26 ULTRAPURE WATER® March 2007--UP240226
converted to insoluble calcium carbon- sure and collapse catastrophically. Dur-
ate (CaCO3) by adjusting water chemis- ing the collapse of cavities, extremely
try. This can be accomplished by strip- high temperature and intensive pressure
ping dissolved CO2 gas from water, add- wave are generated around the cavities.
ing chemicals such as caustic (NaOH) These extreme physical conditions can
and lime (Ca(OH)2, CaO) to raise pH. accelerate chemical reactions, including
When insufficient carbonate alkalinity the precipitation of CaCO3, and rupture
exists, addition of soda ash (Na2CO3) is bacteria cells (6-10).
required to supply the necessary carbon- In this work, a hydrodynamic cavita-
ate ions. The precipitation method relies tion devicea was incorporated into the
on the nucleation and subsequent growth conventional soda ash process to en-
of CaCO3 particles. Therefore, the cal- hance the calcium removal from the ef-
cium removal rate and efficiency can be fluent of fluoride removal process. Test
improved be enhancing the precipitation results reported in the following sections
process. show that this new process can effective-
Hydrodynamic cavitation has been ly accelerate the CaCO3 precipitation
proven as effective to facilitate the pre- and improve the calcium removal effi-
cipitation process. Cavitation is the dy- ciency.
namic process of the formation, growth,
and collapse of micro-sized bubbles in a Materials and Methods
fluid. When static pressure falls below a Test method. Figure 1 shows the test
critical value, cavities start to form and setup. The test tank was equipped with
continue to grow in the fluid. With a a three-blade mixer. The rotation speed
sudden increase in pressure, these cavi- of mixer was kept constant at 148 revo-
ties cannot sustain the surrounding pres- lutions per minute (rpm) to simulate the
TABLE A
Summary of Water Analysis Results for Test Water
Item Unit Concentration
Temperature o
C 2.5-26.0 (17.9)
pH 6.2-8.5 (7.1)
Conductivity μS/cm 2.5-4.9 (3.6)
Alkalinity mg CaCO3/L 22-111 (49)
Ca mg/L 74-359 (170)
Mg mg/L 3.1-4.9 (4.0)
Na mg/L 165-287 (226)
K mg/L 4.8-6.4 (5.6)
F mg/L 7.8-19.5 (12.7)
Cl mg/L 413-548 (481)
NO3 mg/L 255-262 (259)
SO4 mg/L 375-545 (460)
CODCr mg/L 39-81 (56)
T-N mg/L 307-326 (314)
NH4-N mg/L 193-205 (198)
T-P mg/L 0.04-0.14 (0.08)
Note: Values in parentheses are the averaged concentrations.
conventional soda ash process. In the hydrodynamic cavitation
process, the treatment unit withdrew test water from the bottom
of the test tank and returned it to the top. After the test tank was
filled up, certain amounts of Na2CO3 was added to supplement
the necessary alkalinity. The reaction time was limited to 30
minutes for each test. Water samples were collected prior to the
Na2CO3 addition and during the reaction period to monitor the
changes of dissolved calcium and other water chemistry param-
eters.

Treatment unit for hydrodynamic cavitation process.

The treatment capacity of the treatment unit used in this study
was 80 liters per minute (L/min). The treatment unit was Figure 1. An illustration of the hydrodynamic cavitation
designed on the principle of controlled hydrodynamic cavita- process setup.
tion and has been used in cooling water treatment to control
scale, corrosion, and bacterial problems. The unit consists of
a pressure-equalizing chamber and a cavitation chamber. In-
side the cavitation chamber, two pairs of nozzles are positioned
opposite each other — at specific distances, lengths and angles.
Water is first pump into the pressure-equalizing chamber at a
pump pressure of 70 pounds per square inch gauge (psig).
From the equalizing chamber, water is channeled into the
cavitation chamber, where water is forced to rotate at high
velocities. The rotation of water streams creates a high vacu-
um, typically greater than -27.5’ mercury (Hg). This high
vacuum condition causes micro-sized cavities to form in the
water streams. The water streams in two nozzles rotate in
opposite directions. Meanwhile, the water streams travel
forward at high speeds. Upon exiting from the nozzle, the
opposite water streams collide at the mid-point of cavitation
chamber. At this point, pressure increases spontaneously, Figure 2. Calculated alkalinity/calcium hardness ratio in test
causing the sudden implosion of cavities and generating hydro- water.
dynamic cavitation.

Analytical methods. Water chemistry analyses included

pH, conductivity, alkalinity, and hardness. The conductivity
and pH were measured using a Orion 125A+ conductivity
meter (Thermo, U.S.) and an Orion 720A pH meter (Thermo,
U.S.). The alkalinity was determined using the traditional
titrimetric method. The calcium concentration was analyzed
with inductively coupled plasma method (ICP-OES Liberty,
Varian, U.S.). For selected samples, a more detailed analysis
was performed. An ICS-2000 Ion Chromatography (Dionex,
U.S.) was used to measure the inorganic ions; an AA3 Contin-
uous-Flow Wet-Chemical Analyzer (Bran+Luebbe, Germany)
was used to determine total nitrogen, and total phosphorous.
Organic content was measured using the Reactor Digestion
Method (Hach Method 8000). Total suspended solids (TSS) Figure 3. Changes of calcium removal with the hydrodynamic
were estimated with the procedure described in Standard cavitation process treatment frequency.
Methods 2540 D (11). CaCO3 precipitates were collected from
selected runs for particle size distribution analysis using a of 2.5 to 4.9 millisiemens per centimeter (mS/cm) and pH
MastersizerS Particle Analyzer (Malvern Inc., U.K.). changed from 6.2 to 8.5. The calcium concentration was in the
range of 74 to 359 milligrams per liter (mg/L), with an average
Results and Discussion of 170 mg/L and alkalinity was in the range of 22 to 111 mg
Laboratory test. The test water was collected from the CaCO3/L with an average of 49 mg CaCO3/L. Most of calcium
effluent stream of the fluoride removal process at an electronics hardness was in the form of non-carbonate (permanent hard-
manufacturer. Over the course of this test, effluent temperature ness), as indicated by low alkalinity/Ca hardness ratio in Figure
fluctuated from 2.5 to 26.0oC. Conductivity varied in the range 2. The total suspended solids were 0.5 to 5.0 mg/L during the
ULTRAPURE WATER® March 2007--UP240226 27

Figure 4. Changes of Ca removal with Na2CO3 dose.
test period. Table A summarizes the
concentration range and average of the
main constituents in the test waters.
Contents of heavy metals, such as alumi-
num (Al), arsenic (As), barium (Ba),
cadmium (Cd), chromium (Cr), copper
(Cu), iron (Fe), manganese (Mn), lead
(Pb), and strontium (Sr), were usually
below 0.01 mg/L.
Due to high concentration of non-car-
bonated hardness (approximately 80 %,
based on total hardness), the test water
was often under saturated to CaCO3.
Even for effluent with high pH and alka-
linity, the degree of supersaturation was
too low to yield any significant calcium
removal in the form of CaCO3. There-
fore, Na2CO3 was added to supply the
alkalinity and carbonate ions.
Preliminary test results show that for
the hydrodynamic cavitation process, the
calcium removal efficiency was affected
by the process’ treatment frequency. The
most significant improvement was ob-
served when the treatment frequency
was less than 2.0, followed by a much
slower improvement with further in-
crease in the treatment frequency. A
typical change of calcium removal with
the HVC treatment frequency is depict-
ed in Figure 3. In this set of tests,
calcium removal was 40% with the con-
ventional method, but was improved to
70% with the hydrodynamic treatment
frequency at 2.0. The calcium removal
was further increased to 78% with treat-
ment frequency at 4.0. Beyond this
point, the efficiency of calcium removal
28 ULTRAPURE WATER® March 2007--UP240226
Figure 5. CaCO3 particle size distribution in the HVC and
conventional processes.
remained almost unchanged with the
further increase in the treatment fre-
quency. Based on these results, it is
recommended that the hydrodynamic
treatment unit for the process should
have the capacity for treatment frequen-
cy of 2.0 to 4.0.
Although the chemistry of test water
varied over a wide range during the test
period, all test results indicated that the
HVC process can significantly acceler-
ate the precipitation reaction and reduce
the Na2CO3 dose. Figure 4 shows the
typical changes of calcium removal with
Na2CO3 dose observed. On average, the
calcium removal efficiency of 26% was
increased when Na2CO3 was dosed with
the rate of 530 mg/L in feed. To achieve
a 70% calcium removal, amounts of
Na2CO3 required could be reduced near-
ly 20% with the hydrodynamic process.
The enhanced calcium removal by the
hydrodynamic process, at least partially,
is related to the population and size of
CaCO3 particles formed in the water.
Particle size analysis revealed that CaCO3
particles formed in the hydrodynamic
process were much smaller and more
uniform. Selected test results are sum-
marized in Table B and Figure 5. The
average particles size was reduced from
95 micrometer (μm) to 25 μm when the
hydrodynamic cavitation treatment was
applied. The specific surface area of
CaCO3 particles was increased almost
10 times. While CaCO3 particles ranged
from 15 μm to over 170 μm in the con-
ventional soda ash method, most of the
CaCO3 particles were smaller than 55
mm in the hydrodynamic process. The
predominant particles were distributed
narrowly between 15 to 35 μm. It is also
interesting to note that often there was a
secondary peak around 2.5 μm for parti-
cles form the hydrodynamic cavitation
process.
The significant difference in particle
sizes indicates that more CaCO3 parti-
cles were formed in the HVC process.
This is in agreement with previous stud-
ies that hydrodynamic cavitation can
facilitate the nucleation process of CaCO3
precipitation. More CaCO3 nuclei were
formed from the supersaturated solution
in the HVC process by cavitation action.
In addition, it is also possible that some
of the CaCO3 particles were disintegrat-
ed into small pieces under cavitation
action and collision force generated by
the two water streams inside of the HVC
unit. This could be responsible for the
secondary peak shown in Figure 6. Based
on mass balance, it is estimated that the
number of CaCO3 particles formed was
increased at least 50 times by the hydro-
dynamic cavitation process. A high pop-
ulation of CaCO3 particles provided more
active sites for CaCO3 molecules to grow
on. Consequently, the calcium-removal
rate was increased and the added Na2CO3
can be more effectively used within the
reaction period. This relationship is
illustrated in Figure 6 with the assump-
tion of a liner dependence of CaCO3
growth rate on calcium concentration.
Despite the significant differences in

TABLE B
Summary of Particle Size Analysis Results
Operation Mode Hydrodynamic
Process*
Average particle size (mm)
Specific surface area (m2/g) 0.079
Uniformity 2.905 E-01
*See Endnote.
particle size and specific surface area,
there were little differences in the chem-
ical compositions of CaCO3 formed from
the two different processes. All chemi-
cal analyses showed that the calcium
accounted for 99.2% of all cations in the
precipitated CaCO3 particles. Sodium,
magnesium, and aluminum were usually
in the ranges of 0.3 to 0.4%, 0.1 to 0.2%,
and 0.1 to 0.3%, respectively. Very low
concentrations of manganese and iron,
in the range of 0.02 to 0.04%, were also
detected.
Field test of the hydrodynamic cav-
itation process. Based on the labora-
tory tests, the optimum operation condi-
tion and Na2CO3 dose was obtained for
the hydrodynamic cavitation process. A
field test was conducted using the efflu-
ent of the same fluoride removal process
for the above laboratory tests. At this
facility, the effluent from fluoride re-
moval process will be commingled with
organic waste stream and then treated
with bioreactor (MBR) to remove dis-
solved nitrogen. To maintain bioreac-
tor’s efficiency, the calcium concentra-
tion in the mixed wastewater stream is
recommended less than 30 mg/L. Based
on the back-calculation as shown in Fig-
ure 7, the calcium removal from the
effluent of fluoride removal process
should be around 70 %.
Selected field test results are summa-
rized in Figure 8. Despite the wide range
of changes in water chemistry, dissolved
calcium was effectively removed by the
hydrodynamic process. During the sta-
ble operation period, the calcium re-
moval efficiency was maintained at
around 70%, with 63% of removal when
initial calcium concentration was low
and 76% when initial calcium concen-
tration was high.
Conventional
Process*
95 25
0.783
4.005 E-01
Economic analysis. By effective
control of dissolved calcium concentra-
tion in wastewater stream, significant
saving can be achieved by reduce the
maintenance cost on bioreactor mem-
brane. Based on this study, the net present
worth (NPW) analysis shows that the
hydrodynamic cavitation process is more
cost effective than the conventional soda
ash process for application in the elec-
tronics wastewater treatment plant de-
spite of higher initial capital investment.
In addition, the hydrodynamic process
can reduce the reaction time by facilitat-
ing the CaCO3 precipitation reaction and,
therefore, reduce the size of reaction
tank and/or improve the efficiency of
plant operation.
Conclusion
The hydrodynamic cavitation process is
effective to remove dissolved calcium
from wastewater streams. Compared to
the conventional soda ash process, the
hydrodynamic process requires a small-
er sodium carbonate dose and yields
higher calcium removal. The reaction
time can be reduced because of the ac-
celerated CaCO3 precipitation in the
hydrodynamic process, resulting to more
efficient operation of the wastewater
treatment plant. In addition, the water
quality of the effluent is more easily
controlled by the hydrodynamic cavita-
tion process. The net present worth
(NPW) analysis shows that the hydrody-
namic process can be more cost effec-
tive than the conventional process for
application in the electronics wastewa-
ter treatment.
Acknowledgements
This research was supported by a grant
( I2 WATERTECH 04-06) from
ULTRAPURE WATER® March 2007--UP240226
WaterTech of Eco-STAR project fund-
I2
ed by Ministry of Environment, South
Korea.■
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29

Figure 6. Changes of calcium removal and CaCO3 particle size
with time in batch treatment for different CaCO3 particle
concentration (Solid line for high concentration and dashed line
for low concentration) (12).
Figure 7. Estimated calcium budget in the wastewater treatment
plant.
Figure 8. Calcium removal efficiency of the hydrodynamic
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Endnote
a
The hydrodynamic cavitation device referred to in the text is from VRTX
Technologies of San Antonio, Texas. The process is known as the Hyperki-
netic VRTX Crystallization (HVC) and is used to accelerate CaCO3 precip-
itation.
30 ULTRAPURE WATER® March 2007--UP240226
Author Sun-Jip Kim, Ph.D., is a chief of Central Research
Center at G&G Co, Ltd. He has 20 years of experience in
development and application of water and wastewater treat-
ment procesess. He holds a doctorate from Konkuk University
in South Korea and is a member of IEC and KSEE.
Coauthor Jin-Young Park is a researcher of Central Re-
search Center at G&G Co. and has 4 years of experience in
development and application of water and wastewater treat-
ment processes.
Coauthor Won-Kwon Lee, Ph.D., is CEO at G&G Co. and
has 24 years of experience in development and application of
industrial water treatment processes. He holds a doctorate
from Hanyang University in South Korea.
Coauthor Wiley Wang, Ph.D., is senior chemist at VRTX
Technologies LLC. He has 16 years of experience in water
chemistry, water treatment product developments and appli-
cations, laboratory and field testing, and evaluations. He
holds a doctorate from Texas A&M University and is an active
member of NACE, AIChE,, and ACS.
Coauthor Yong-Woo Lee, Ph.D., is a general manager of
Samsung Engineering Co. Ltd. and is in charge of environ-
mental technology development at the R&D Center. He has 21
years of experience in advanced domestic and industrial
wastewater treatment, and reuse systems. He received his
doctorate. at Polytechnic University and is an active member
of IWA, KSEE, KSWQ, and KIEC.
Coautho Kyu-Won Hwang is a manager of water treatment
team at Samsung Electronics. He has 9 years of experience in
construction and operation of water and wastewater treatment
system.
Key words: SEMICONDUCTORS, WASTEWATER