Selective Fluoride Removal

By Kedar Oke, Dr. Stefan Neumann, & Beryn Adams

Fluoride concentrations of less than one milligram per liter can Principle Of The Process
easily be achieved by utilization of a new adsorption method The fluoride selective ion exchange resin is a chelating resin
based on a regenerable aluminum doped chelating resin. A case loaded with aluminum ions. The functional group of the resin
study illustrates practical aspects of the implementation and lab is an amino-methyl-phosphonic-acid-group, or AMPA-group.
The phosphonic acid group has a high tendency to bind
data gives more technical background on important parameters
aluminum. This strong binding force can be deduced from the
for process design. fact that aluminum-phosphate has a low solubility in water.
The AMPA-resin was chosen as the most suitable resin for this
Introduction application since it tightly binds the aluminum, resulting in low
Fluorides are found in the waste discharges from process streams leakage of aluminum during operation. The theoretical structure
in a number of industries. Significant amounts of fluoride come of the AMPA functional group loaded with aluminum-chloride
from the following industries: semiconductor, photovoltaic, is shown below in Figure 1.
glass manufacturers, electroplating, steel and aluminum,
It is significant that the aluminum ion is connected with
pesticides and fertilizer. The fluoride concentration in untreated
two binding arms towards the AMPA-group, while the
effluent can vary over a large range, and the allowable level for
third binding arm of the aluminum core is attached to one
discharge depends on the place of disposal. When there is any
chloride ion. In contact with fluoride containing solutions the
risk of fluoride seeping back to water supplies, a limitation of
chloride is exchanged by fluoride. Other ions such as sulfate
around one ppm fluoride is typical. Apart from treatment of
or nitrate do not interact with the aluminum ion since their
industrial waste streams, the other main application of fluoride
affinity to aluminum is very low (this can be deduced from the
removal is the treatment of potable water supplies to reduce
high solubility of aluminum sulfate and aluminum nitrate in
the fluoride content to 1 ppm or less.
solution).
High levels of fluoride are generally reduced by adding calcium
One liter of Lewatit MonoPlus® TP260 can be doped with
salts, causing precipitation of CaF2. However due to certain
approximately 1.1 mole of aluminum. Supposing every
rest-solubility and kinetic effects the fluoride concentration
aluminum ion absorbs one fluoride ion, the maximum
after precipitation is normally 7–15 mg/L, higher than the
theoretical uptake (total capacity) of fluoride is about 21 g/L.
acceptable limits. Since pollution control boards typically
As usual, operating capacities experienced under operating
require an effluent limit of 1 mg/L fluoride, these saturated
conditions are significantly lower than this.
CaF2 solutions must undergo further treatment. There are two
known treatment processes: After exhaustion of the resin, the regeneration can be carried
out using aluminum chloride solutions (a solution of AlCl3
1) Adsorption on activated alumina
or AlCl3*6H2O). The Al3+ will form several complexes with
2) Removal by selective ion exchange resin fluoride in solution, such as [AlF]2+, [AlF2]+, [AlF(OH)]+,
[AlF4]- and others. These compete with the fluoride fixed on
In this article we will be focusing on removal of fluoride by a the functional group of the resin. Due to effects of mass action
fluoride selective ion exchange resin. and shift of equilibrium the fluoride is extracted from the resin

76 Water Today l May - 2011

 and exchanged by chloride. Hence after the treatment with the
AlCl3 solution the resin is still in the aluminum loaded form
with a chloride-ion connected to it.

After this operation, the spent regenerant solution containing

aluminum salt and fluoride can be treated by precipitation.
Usually this is done by adding milk of lime into the weakly
acidic waste water: the aluminum will precipitate as aluminum
hydroxide, while fluoride will form CaF2 and Al(OH)2F. The
Figure 1: Functional Group Of The AMPA-Resin Lewatit Monoplus®
TP 260 After Loading With Aluminum-Chloride precipitated solids can be filtered and sent to landfill.

In case the ion exchanger is used as a polishing filter behind a

lime precipitation unit, the spent regenerant can be discharged
into this unit and no extra spent regeneration treatment
unit is required. Hereby the excess aluminum coming from
the ion exchanger unit can support the performance of the
precipitation unit and partially substitute the chemical dosage
required there.

The whole operating cycle is schematically depicted in figure

2. The concept of a precipitation unit followed by the ion
exchanger as a polishing filter is shown in figure 3.

Case Study
Technical Equipment / Plant Concept /Performance
Figure 2: Reaction Scheme Of The Selective Fluoride Removal By
Aluminum Doped Lewatit Monoplus® TP 260 A unit containing Lewatit MonoPlus® TP 260 resin has been
installed in a major chemical manufacturing company in
Gujarat, India. It has been reliably treating the full effluent
stream of a production facility for more than a year and is still
operating successfully. The plant has consistently maintained
the fluoride level in the treated effluent to less than 1 mg/L. A
photo of the plant is given in figure 4.

The concept of the plant comprises initial precipitation of

the fluoride with CaCl2 followed by filtration. The filtrate is
polished with the ion exchanger. The effluent stream flow is
around 1.5 m³/h. The CaCl2 precipitation process reduces the
fluoride content from around 100 mg/l down to 8 – 18 mg/l.

Fluoride feed concentration: 9 mg/L; feed pH = 5.8; specific

flow rate 5 BV/h; salt background (TDS) high due to
Figure 3: Principle Of Using Fluoride Selective Resin As A Polishing precipitation upstream but not determined.
Filter Unit Behind CaF2 Precipitation

Water Today l May - 2011 77

In this plant there is a single ion exchange filter, containing 300 and the suspended particles are settled. The sludge is then
liters of resin. A representative filtration curve is shown in figure thickened and finally dewatered in a filter press.
5. It can be concluded from the curve that the break through
of fluoride at 1 ppm occurred after 286 BV, which equals 57 The user of the plant takes advantage from the following
hours of operation. With an influent fluoride concentration of benefits:
9 mg/l, the operating capacity of the filter is therefore about
2.6 grams of fluoride adsorbed per liter of resin. • Able to safely meet the pollution control board norms for
waste water discharge
After break through the filter is regenerated by pumping 3 BV
• Synergism with the upstream precipitation unit: no
of a 5.5% AlCl3 solution down through the bed at 5 BV/h.
additional waste stream generated, as the spent regenerant
The operation is followed by a 10 min upstream rinse at 10
from the ion exchanger is treated using the existing on-site
m/h linear velocity and a final rinse by 2.5 BV of clean water
process
at 5 BV/h.
• Regenerable adsorber material that can stay in place for
The ion exchange wastewater (comprising spent regenerant, several years
backwash and final-rinse water) is discharged into a cone shaped
tank equipped with an agitator, pH control and CaCl2, H2SO4 Results Of Lab-Tests On Ion Exchange Based
and NaOH dosage. Fluoride and aluminum are precipitated Fluoride Removal
Complementary laboratory tests were conducted during the
development of this technology for selective fluoride removal.
This generated interesting data and in particular gave insights
into the influence of fluoride-concentration, pH and salt
content of the feed solution on the operating capacity.

Figure 6 demonstrates operating capacities as a function of feed

concentration under two different salt background conditions.
As usual the operating capacity increases with increased feed
concentration, which is normal for adsorption processes.
Secondly, it was found that operating capacities are higher in
cases where the salt content in the feed is higher. This is a
quite unexpected result since typically the operating capacity
decreases with higher concentration of competing ions.

We propose the explanation that higher salt concentrations in

solution increase the proportion of aluminum ions (shown in
Figure 1) having one binding leg attached to a dissolved ion,
making it available for exchange of fluoride (according to the
scheme given in Figure 2). If there is less salt in the background
the aluminum ion in the complex tends more to coordinate to
the resin functional groups with all three binding legs. In that
configuration the aluminum seems to have a lower tendency to
adsorb fluoride.

Figure 4: Fluoride Selective Ion Exchanger Operated At A Major

Figure 7 shows the effect of pH on the operating capacity
Chemicals Manufacturing Company In Gujarat, India measured under low salt background conditions. Here it was

78 Water Today l May - 2011

 Figure 5: Original Filtration Curve Generated From Data Measured Figure 7: Effect of pH on fluoride operating capacity. SV = 10 BV/h,
At The Gujarat Reference Plant. 1.2 moles of Al3+ doped per liter of resin Lewatit MonoPlus® TP 260,
concentration of fluoride in feed = 127 mg/L, demineralized water
background
found that the operating capacity is highest under weakly acidic
conditions (pH = 4) and decreases roughly by 50% in weakly more projects utilizing this process will be commissioned
alkaline conditions (pH = 10). Hence it can be concluded in India. Further work is planned to investigate reducing
that slightly acidic to neutral conditions in the feed water are aluminum consumption during regeneration. While already an
favorable for the process. economically attractive process, this should lead to reductions
in operational cost as well.
Conclusion & Outlook
Further Laboratory work is underway to adapt the process
The plant experience referenced has been very successful and to make it suitable for potable water applications. As Lewatit
as a result other factories are investing in resin based treatment MonoPlus® TP 207 has approval for use with drinking water; it
to solve their wastewater problems. In the near future is used in place of Lewatit MonoPlus® TP 260. The application
method and performance is comparable when using Lewatit
MonoPlus® TP 207, leading to very optimistic expectations
about the potential. The initial aluminum leakage of the freshly
regenerated column can be successfully removed by a polishing
column behind the fluoride selective filters.

About The Authors

Kedar Oke works at LANXESS India Private Limited, Business Unit

Ion Exchange Resins. He can be reached at [email protected]

Dr. Stefan Neumann works at LANXESS Deutschland GmbH,

Figure 6: Effect of feed concentration on operating capacity under Business Unit Ion Exchange Resins. He can be reached at stefan.
two different operating conditions: With 10 g/L total dissolved [email protected]
solids (TDS) in the background and with demineralized water
background(0 g/L TDS). Specific Velocity (SV) = 10 BV/h, 1.3 moles Beryn Adams works at LANXESS Pte. Ltd. He can be reached at
of Al3+ doped per liter of resin Lewatit MonoPlus® TP 260, feed pH =
3.6; salt mixture for TDS background containing 50% p.w. NaCl and [email protected]
50% Na2SO4.

80 Water Today l May - 2011