Boron Removal From Shat Al-Arab River Water Using Electrocoagulation
Boron Removal From Shat Al-Arab River Water Using Electrocoagulation
Boron Removal From Shat Al-Arab River Water Using Electrocoagulation
13, 2012
ABSTRACT
Shat Al-Arab is a river located at the south of Iraq. Boron concentration has
increased significantly recently due to the drought season which makes water from
the Arabian Gulf pour into Shat Al-Arab. Boron concentration, as high as 5 mg/l,
was detected in this river. This is 10 times the allowable drinking water concentration
for boron according to WHO and the Iraqi drinking water guidelines, i.e. 0.5 mg/l.
Experiments were conducted to determine the ability of electrocoagulation
technique to reduce boron concentrations in synthetic water of 5 mg Boron/l and
conductivity of 2000 µS/cm to the required level in drinking water. Experimental
setup was prepared to determine the effects of several operating parameters on the
optimum operation for the electrocoagulation. In addition, the technique was
compared with chemical coagulation, using Poly-Aluminum-Chloride, Aluminum
Sulphate, and Ferric Chloride.
The experiments revealed that chemical coagulation has a very low efficiency
(about 12%) that renders it unsuitable as a pretreatment for existing (or for the future)
desalination units. On the other hand, electrocoagulation experiments showed a
maximum boron removal efficiency of 40% at a current density of 5 mA/cm2,
operating time of 30 minutes, and pH of 8.
اﻟﺨﻼﺻﺔ
وﻗﺪ زاد ﻓﻲ اﻵوﻧﺔ اﻷﺧﯿﺮة ﺗﺮﻛﯿﺰ اﻟﺒﻮرون ﻓﻲ ﻣﯿﺎھﮫ،ﺷﻂ اﻟﻌﺮب ھﻮ ﻧﮭﺮ ﯾﻘﻊ ﻓﻲ ﺟﻨﻮب اﻟﻌﺮاق
ﺗﻢ اﻟﻜﺸﻒ ﻋﻦ.ﺑﺸﻜﻞ ﻣﻠﺤﻮظ ﺑﺴﺒﺐ ﻣﻮﺳﻢ اﻟﺠﻔﺎف اﻟﺬي ﺟﻌﻞ ﻣﯿﺎه ﺧﻠﯿﺞ اﻟﻌﺮﺑﻲ ﺗﺼﺐ ﻓﻲ ﺷﻂ اﻟﻌﺮب
أﺿﻌﺎﻓﺎﻟﺘﺮﻛﯿﺰ10 وﯾﺒﻠﻎ ھﺬا،ﻟﺘﺮ/ ﻣﻠﻐﻢ5 اﻟﺒﻮرون ﻓﻲ ﻣﯿﺎه اﻟﻨﮭﺮ وﻟﻮﺣﻆ وﺟﻮد ﺗﺮﻛﯿﺰ ﻋﺎﻟﻲ ﯾﺼﻞ إﻟﻰ
اﻟﻤﺴﻤﻮح ﺑﮫ ﻓﻲ ﻣﯿﺎه اﻟﺸﺮب وﻓﻘﺎ ﻟﻤﻨﻈﻤﺔ اﻟﺼﺤﺔ اﻟﻌﺎﻟﻤﯿﺔ واﻟﻤﻮاﺻﻔﺔ اﻟﻘﯿﺎﺳﯿﺔ ﻟﻤﯿﺎه اﻟﺸﺮب ﻓﻲ اﻟﻌﺮاق
.(ﻟﺘﺮ/ ﻣﻠﻐﻢ0.5 ) واﻟﺒﺎﻟﻐﺔ
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ﺗﻢ إﺟﺮاء ﺗﺠﺎرب ﻟﺘﺤﺪﯾﺪ ﻗﺪرة ﺗﻘﻨﯿﺔ اﻟﺘﺨﺜﯿﺮ اﻟﻜﮭﺮﺑﺎﺋﻲ ﻋﻠﻰ ﺧﻔﺾ اﻟﺒﻮرون ﻓﻲ ﻣﯿﺎه ﺻﻨﺎﻋﯿﺔ ﺗﺤﺘ ﻮي
ﺳﻢ إﻟ ﻰ اﻟﺤ ﺪود اﻟﻤﺴ ﻤﻮح ﺑﮭ ﺎ/ ﻣﯿﻜﺮو ﺳﯿﻤﻨﺰ2000 ﻟﺘﺮ ﺑﻮرون وﺗﻮﺻﯿﻠﯿﺔ ﻣﻘﺪارھﺎ/ ﻣﻠﻐﻢ5 ﻋﻠﻰ ﺗﺮﻛﯿﺰ
ﺗﻢ إﻋﺪاد اﻟﺘﺠﺎرب ﻟﺘﺤﺪﯾﺪ اﻵﺛﺎر اﻟﻤﺘﺮﺗﺒﺔ ﻋﻠﻰ ﻋﺪد ﻣ ﻦ اﻟﻤﻌ ﺎﯾﯿﺮ ﻋﻠ ﻰ اﻟﺘﺸ ﻐﯿﻞ اﻷﻣﺜ ﻞ.ﻓﻲ ﻣﯿﺎه اﻟﺸﺮب
، ﺗﻤ ﺖ ﻣﻘﺎرﻧ ﺔ ھ ﺬه اﻟﺘﻘﻨﯿ ﺔ ﻣ ﻊ ﺗﻘﻨﯿ ﺔ اﻟﺘﺨﺜﯿ ﺮ اﻟﻜﯿﻤﯿ ﺎﺋﻲ اﻟﺘﻘﻠﯿﺪﯾ ﺔ، ﺑﺎﻹﺿﺎﻓﺔ إﻟ ﻰ ذﻟ ﻚ.ﻟﻠﺘﺨﺜﯿﺮ اﻟﻜﮭﺮﺑﺎﺋﻲ
وﻛﻠﻮرﯾﺪ، و ﻛﺒﺮﯾﺘﺎت اﻷﻟﻮﻣﻨﯿﻮم،وذﻟﻚ ﺑﺎﺳﺘﺨﺪام ﺛﻼث أﻧﻮاع ﻣﻦ اﻟﻤﺨﺜﺮات؛ ھﻲ ﺑﻮﻟﻲ ﻛﻠﻮرﯾﺪ اﻻﻟﻤﻨﯿﻮم
( ﻣﻤ ﺎ ﯾﺠﻌ ﻞ ھ ﺬه%12 ﻛﺸﻔﺖ اﻟﺘﺠﺎرب أن ﻟﻠﺘﺨﺜﯿﺮ اﻟﻜﯿﻤﯿﺎوي ﻛﻔﺎءة ﻣﻨﺨﻔﻀﺔ ﻟﻠﻐﺎﯾﺔ )ﺣﻮاﻟﻲ.اﻟﺤﺪﯾﺪﯾﻚ
ﻣ ﻦ ﻧﺎﺣﯿ ﺔ.(اﻟﺘﻘﻨﯿﺔ ﻏﯿﺮ ﺻﺎﻟﺤﺔ ﻟﻼﺳﺘﻌﻤﺎل ﻛﻤﻌﺎﻟﺠﺔ أوﻟﯿﺔ ﻟﻮﺣ ﺪات ﺗﺤﻠﯿ ﺔ اﻟﻤﯿ ﺎه اﻟﻘﺎﺋﻤ ﺔ )أو اﻟﻤﺴ ﺘﻘﺒﻠﯿﺔ
ﻋﻨ ﺪ اﺳ ﺘﺨﺪام%40 أﻇﮭﺮت ﺗﺠﺎرب اﻟﺘﺨﺜﯿﺮ اﻟﻜﮭﺮﺑﺎﺋﻲ ﻹزاﻟﺔ اﻟﺒﻮرون ﻛﻔ ﺎءة ﻋﻀ ﻤﻰ ﺑﻤﻘ ﺪار،أﺧﺮى
.8 ( ﻣﻘﺪارھﺎpH) دﻗﯿﻘﺔ و داﻟﺔ ﺣﻤﻀﯿﺔ30 ووﻗﺖ ﺗﺸﻐﯿﻞ،2 ﺳﻢ/ ﻣﻠﻲ اﻣﺒﯿﺮ2 ﺗﯿﺎر ﻛﮭﺮﺑﺎﺋﻲ ﺑﻜﺜﺎﻓﺔ
INTRODUCTION
B
oron is a naturally occurring element that is widely distributed at low
concentrations in the environment. Unlike most of the elements in sea water,
boron is not ionized (i.e. it has no charge). Boron takes two forms in water
(depending on pH value), Boric acid and borate ion. Boric acid dissociation is a
function of pH, above pH 9.24 the anion B(OH)- is predominant, while below pH 9
the uncharged species is predominant [1,2,3]. Boric acid and borate salt have
extensive industrial use in the manufacture of glass and porcelain, in wire drawing,
production of leather, carpet and photographic chemicals.
Although boron is essential for plant growth, in excess of 2.0 mg/l in irrigation
water, it is harmful to certain plants. Other plants may be affected adversely by
concentration as low as 1.0 mg/l [4]. Food and agriculture organization in United
Nations (FAO) imposed a regulation on the concentration of boron in irrigation water
to be between 0.7-3 mg/l [5]. The world health organization (WHO) recommends a
maximum boron concentration as low as 0.5 mg/l for drinking water. Iraqi drinking
water guideline adopted the same value [6].
Several technologies have been used to lower boron concentration in water and
wastewater. One of the important technologies used successfully for this purpose is
electrocoagulation (EC).
In its simplest form, an EC reactor may be made up of an electrolytic cell with one
anode and one cathode [7]. When connected to an external power source, the anode
material will electrochemically corrode due to oxidation, while the cathode will be
subjected to passivation. A simple arrangement of an EC cell with an anode and a
cathode in parallel arrangement is shown in Figure-1. A current is passed through a
metal electrode (Aluminum in this work), oxidizing the metal (M) to its cation (Mn+),
while water is reduced to hydrogen gas and the hydroxyl ion (OH-), as can be seen in
these equations:
→ + ….. (1)
2 +2 → 2 + ….. (2)
The theoretical amount of dissolved materials (m) can be calculated using Faraday’s
second law:
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= ..... (3)
Where n is the number of electrons transferred in the reaction at the electrode, M the
molecular weight (g/mol), I is current flow and F is Faraday’s constant (96,486
C/mol) and t is the time.
There are a variety of ways in which species can interact in solution, the inherent
complexity of the process makes it difficult to model and control [8]. In brief three
stages are developed in series in electrocoagulation. Initially the metal cations
(Aluminum in this work) contribute to charge neutralization of the pollutant particles
as the isoelectric point is attained. Here, a sorption coagulation mechanism occurs
resulting in the formation of loose aggregates. As time progresses, further aluminum
cation addition results in amorphous aluminum hydroxide precipitation that promotes
pollutant aggregation via a sweep coagulation mechanism. During the final stages,
coagulated aggregates interact with bubbles and float to the surface or settle to the
bottom of the reactor [7].
Technologies for boron removal include conventional and advanced treatment
technologies such as, chemical precipitation, ion exchange, reverse osmosis (RO),
adsorption with Activated Carbon (AC), and Electro-dialysis (ED).
In chemical precipitation, there are several precipitants to be used for boron removal
including metal salts such as the salts of calcium, magnesium, aluminum, manganese,
iron(II), iron(III). Chemical precipitation could effectively remove boron but requires
adjusting water pH to a high level, greater than 9. Therefore, this method causes high
salinity and produces a voluminous amount of sludge for disposal. That cause a high
costs for chemical demands and sludge disposal. These costs sometime prohibit the
use of chemical precipitation for boron removal [9].
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RO and ED are effective in removing boron from seawater for drinking water
purpose. But there are disadvantages in these methods which are, producing brine
water waste, the requirement of high pressures for multiple stages RO and thus high
energy costs, raising pH greater than 11 results in the membrane scale/fouling
problems, costly maintenance and replacement of membranes, and the need of full
pretreatment process contribute significantly to total production cost [10]. Single
stage SWRO membranes are able to reduce boron concentrations from sea water to
about 0.9–1.8 mg/L in permeate. In some particular cases, however, even a two stage
RO process working at normal operation conditions, is insufficient for reducing boron
concentrations to the level that meets the drinking water quality requirements [11,12].
The principle of electrocoagulation was first patented in 1887 by Eugene Hermite
[13]. He received two British and French patents which described a method of
treating sewage by mixing with a proportion of seawater and electrolyzing. A
treatment plant utilizing these patents was built in 1889 in London and operated for
10 years. In the same year, another plant for treating canal water was built in Salford,
England. Iron electrodes were used and seawater added as a chlorine source for
disinfection. In 1909, a patent for the purification of wastewater by electrolysis using
aluminum and iron corroding electrodes was established in the USA [8]. Electrolytic
sludge treatment plants were in operation as early as 1911 in Santa Monica,
California and Oklahoma City. In 1925, the electrocoagulation of water purification
with a soluble iron anode was first used at the Shature Power Station in the Soviet
Union [13]. Mohammad and Muttucumaru published an excellent review for the
application of EC to pollutant removal [14].
Iraq is one of the arid and semi-arid countries. For several years, Iraq has suffered
from severe drought conditions. This leads to a significant reduction in surface water
quantities and deterioration of its quality. As the level of fresh water flowing into
Shatt al-Arab from the Euphrates and Tigris Rivers has declined, salty water from the
Arabian Gulf has increasingly dispersed in it. This leads to increase the salt levels in
several locations in Shatt-Alarab to high concentrations (TDS>10000 mg/l). Salt
water flowing into the waterways renders the water unusable for agricultural
purposes. Boron concentrations increased to reach a level of around 5 mg/l, which is
10 times the allowable content by WHO and by the Iraqi drinking water guideline [6].
ELECTROCOAGULATION EXPERIMENTS
A laboratory-scale batch reactor (1 liter volume beaker), made of glass was used in
electrocoagulation experiments. Aluminum electrodes, cathodes and anodes, were
fixed vertically in the beaker. The two plates are identical and each with a surface
area of 40 cm2 and 1 mm thick. The net space between the electrodes was 5 mm.
They were connected to terminals of a direct current power supply characterized by
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the ranges 0–5A for current and 0–50V for voltage. Suspensions were stirred using a
magnetic stirrer adjusted to an optimal rate (300 rpm) in order to attain the highest
efficiency of turbidity removal [15]. Before the experiments, the electrodes were
thoroughly cleaned and immersed in 1% HCl for 0.5 h [16].
At the beginning of each experiment the solution of boron of the desired
concentration fed into the reactor. Each experiment was timed starting with the DC
power supply switching on. Electrical conductivity, pH and temperature were all
measured using a WTW multi-meter. Boron concentration was measured according to
the standard method No. 4500B using the Curcumin method, while Aluminum
concentration was measured according to the standard method No. 3500Al using
Eriochrome Cyanine [4]. Electrocoagulation experiment setup is shown in Fig.-2.
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cost for the process. The effects of current densities of (1, 3, 5 and 7 mA/cm2) and
operating time on boron removal percentage are shown in Figure-3.
For the applied range of current density, it was noticed that the boron removal
efficiency keeps on increasing as current increases and as time increases. This was
expected from Faraday’s second law. After 30 min, the reduction rate becomes small
and it will be costly to keep on the system runs after that. A time of 30 minutes was
used by many other authors [14.15,16,18]. A current density of 5 mA/cm2 has a good
boron removal efficiency of 40% after 30 minutes operating time. This value was
used in all other electrocoagulation experiments. Although, this value of current
density came in consistence with other researchers [16,19], boron removal efficiency
is lower than expectation.
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CD=5 mA/cm2
Time= 30 min
pH= 7
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From this figure, it is clear that PACl has a higher removal efficiency than both
Ferric chloride and aluminum sulfate. However, along the applied dosage range, all
the three coagulant showed low boron removal efficiency (max. 13%). This
efficiency is very low and cannot be applied in the desalination pretreatment because
boron concentration will not be changed much.
In order to enhance the PACl efficiency in removing boron, water pH was increased
from 8 to 9. This will, theoretically, shift the boron in water toward the ionized borate
forms. However, the results obtained in Figure-8 showed that Boron removal
efficiency is even worse and reduced by about 70%. This is probably due to the effect
pH on the solubility of aluminum ions in water.
Turbidity target of 5 NTU was achieved after a dosage of about 15 mg/l PACl. At
this dosage, Boron removal percentage was 11% and 3% for pH of 8 and 9
respectively. These results came in consistent with other researchers [18].
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CONCLUSIONS
1- Chemical coagulation is not efficient to remove boron from surface water no
matter what type and quantity of coagulants are used.
2- Electrocoagulation is a better technology to remove boron from surface water and
it can be used as a pretreatment technology ahead of the existing RO desalination
units in the south of Iraq to reduce the overall final boron concentration in the
plants permeated water.
3- Boron removal efficiency obtained in this research was less than those published
in the literature with similar operating parameters. Operation at current density of
5 mA/cm2, time of 0.5 h and pH of 8 yields boron removal percentage of 40%.
4- Power consumption decreases with increasing water conductivity, which is the
case in the south of Iraq. It is expected that the operation cost of the desalination
units at such conditions will be about10%.
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