Manganese Removal Suez Water Handbook

Specifics Water treatment manganese removal - Degremont® Page 1 of 13

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natural states

Manganese is an element that is often found in the ground. Many manganese ores can
be found, mainly oxides (pyrolusite, vernadite, etc.) and occasionally carbonates
(rhodochrosite), silicates, sulphides, etc.
In natural water, manganese will usually be present in the soluble ionised form, Mn2+,
and sometimes as MnOH+ (very basic pH). It can form compounds with the
bicarbonates, sulphates and silicates present at the same time and also with some
types of OM (humic and fulvic acids). Manganese will often be present in natural water
in combination with iron and ammonium. However, there are cases where the
manganese is present on its own.
physical-chemical removal of manganese
Figure 30 provides a stability diagram for the most common forms of manganese.
Figure 30. Manganese stability diagram
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oxidation using oxygen
Manganese Mn2+ is very slowly oxidised by oxygen to form MnO2 according to the
following kinetics:
Oxidation using oxygen only reaches an appreciable rate when the pH rises above 9.5
(figure 31). Mn2+ oxidation using oxygen depends on temperature: oxidation will be 5
times faster when the temperature rises from 11°C to 22°C; however, at normal pH
levels, contact times are not easily compatible with industrial operation.
The presence of manganese dioxide "catalyses" the reaction. This has been recorded
in the case of some plants operating at a high pH where, after a certain time operating
with other oxidants, sand is coated with a MnO2 deposit. However, this effect will not be
enough to produce treated water that is completely manganese-freee.
Figure 31. Mn2+ removal by oxygenation
oxidation using MnO2
It has also been found that, at lower pH, MnO2 ceases to act as a catalyst but
becomes an oxidant according to the following reaction :
In such cases, the MnO2 needs to be regenerated at regular intervals using

permanganate :
The overall balance for reactions (1) and (2) will be :
In practice, instead of ‘manganising’ sand, it is advisable to use a filtering medium

made up of MnO2("green manganised sand", "polarite "…) that can be mixed in greater
or lesser amounts with the sand and which will also require regeneration at regular
intervals.
oxidation using chlorine
Chlorine does not provide better oxidation of manganese than oxygen at a pH < 9.5;
however, these same filtration mixes can be used (pH ≥ 8) as catalysts when oxidising
Mn2+ using chlorine, occasionally after sedimentation and an initial filtration in an acid
medium for the purpose of removing OM (case of some soft and coloured surface
water).
oxidation using chlorine dioxide
As already reviewed in the section oxidation and reduction (/water-and-

generalities/fundamental-physical-chemical-engineering-processes-applicable-
to-water-treatment/oxidation-and-reduction), this is a relatively slow reaction and, in
the presence of OM, produces chlorites; therefore, it is not recommended.
oxidation using potassium permanganate
Oxidation-reduction occurs between manganous manganese and permanganate

according to reaction (3) above.
Therefore, it will be seen that KMnO4 consumption remains the same as when MnO2
oxidation regenerated by KMnO4 is included as an interim step; the advantage of the
latter method is that it provides a "regulator" in cases where the Mn2+ concentration
fluctuates, enabling us to dispense a constant amount of KMnO4 set to an average
level ("continuous regeneration").
The theoretical proportion is 1.9 g of KmnO4 to 1 g of Mn. However, in practice, the

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effect, a proportion of the permanganate is involved in the oxidation of some reducing
OM present in water. Additionally the amount injected must be very carefully controlled:
any excess of KMnO4 will tint water pink, turning to yellow in the mains distribution
system.
If the manganese is not complexed, optimum pH will be in the region of 7.2-7.3 for a
contact time of less than 5 minutes. When the manganese is complexed with OM, the
reaction time can be as long as 20 minutes. In such cases, pH can be adjusted higher
than 8.5 in order to accelerate the reaction.
In actual fact, KmnO4 is the most widely used reagent in physical-chemical manganese
removal. In groundwater applications, plant design will be the same as for simple iron
removal (figures 22 and 23); whether the water contains manganese only or
manganese and iron, the first step will be an aeration (gravity or pressurised) which is
always essential to have an effect on easily oxidised substances (Fe2+ , H2S…) and to
enrich the water with dissolved O2 (protecting the mains against corrosion and
unpleasant odours); permanganate will then be injected, as in the case of any other
reagent used, between aeration and filtration (the latter occurring at the same
velocities, but using finer sand if the water only contains manganese: ES = 0.55 to 0.75
mm).
In soft, coloured surface water applications that contain high amounts of OM and that
require total clarification using coagulation-flocculation and sedimentation (water from
granite areas of primary massives, for instance), the relevant treatment system can be
designed on the basis of the scheme shown in figure 32, constituting an alternative to
the system referred to earlier using chlorine and a "manganised" filtration medium.
Figure 32. Scheme for removing manganese from soft, coloured surface water
9,600 m3 · j–1
Oxidising the manganous ion Mn2+ using ozone is a fast method. The following reaction
applies:
to oxidise 1 g of Mn2+,0.9 g of ozone is required . The amount of ozone injected must

be such that only Mn2+ is oxidised to produce MnO2 without leaving any excess (pink
coloration, etc.), see section oxidation and disinfection using ozone (/processes-
and-technologies/oxidation-disinfection/oxidation-and-disinfection-using-
ozone)).
The Jonchay DWTP (France) is based on this principle (figure 33).
Figure 33. Schematic diagram of the Jonchay DWTP (Rhône, France) – Manganese
removal – Capacity: 14,500 m3 · j–1
When manganese is complexed with OM and requires comprehensive clarification

using coagulation-flocculation-sedimentation, ozone cannot be used as a pre-oxidising
reagent for oxidising manganese. In effect, ozone will only oxidise manganese after
are two ways in which manganese can be removed: either using KmnO4 before
MnO2 precipitate formed being screened out by the filters.
biological removal of manganese – the Mangazur process
principle
As in the case of iron, many bacteria (see section iron and manganese cycle (/water-
and-generalities/what-water-should-we-treat-and-why/natural-water/iron-and-
manganese-cycle)) to biologically oxidise manganese in an aerobic environment.
With some bacteria, oxidation of the Mn2+ will occur indirectly: this oxidation is caused
by an increased pH linked to the growth of these bacteria, ensuring that Mn2+ will be
oxidised by the oxygen at an appreciable rate. For other bacteria, oxidation is caused
by the action of an intracellular enzyme. Finally, for others, dissolved manganese will
begin to be adsorbed on the surface of the cell membrane. It will then be oxidised via
enzymes. The manganese will then be concentrated in a sheath that surrounds the cell
or group of cells.
In order to grow, these bacteria require a relatively basic environement (pH > 7.5),
where the EH must be higher than 400 mV (equivalent to water close to dissolved O2
saturation); please refer to figure 28 and biological manganese removal domain (2). On
the other hand, should the redox potential decrease significantly, some of these
bacteria will solubilise (MnO2, Mn2+ passage) the manganese that they had previously
accumulated.
Similarly, in the presence of easily assimilated OM, bacteria bound with carbon can
compete for dissolved oxygen consumption with those bound with Mn; this may result
in a drop on EH and a release of Mn2+, for instance during shutdown periods.
advantages of biological manganese removal
reagents
to use an oxidant, usually potassium permanganate, when starting up.

Contact time will be brief with most types of water. This is the time required to raise the
redox potential. Aeration can be undertaken in-line (pressurised) or by cascade
(gravity).
filtration rate
As in the case of biological iron removal, the solid nature of the biological floc allows for
the use of high filtration rates which can, in some cases, reach 30-40 m · h–1, through
filtering media of a higher effective size (ES = 1.35 mm) than those used for physical-
chemical manganese removal.
retention capacity
Retention capacity is 5 to 10 times higher than in physical-chemical treatment
operations.
backwash
The backwash can be carried out using raw water (or non-chlorinated treated water).
sludge
Sludge is easily thickened and dewatered.
utilisation
The process and the biological reactor-filter in which it takes place are both called
Mangazur. The pressurised plant is the most frequently adopted solution (except in
high throughput cases) as in the case of Sorgues (Rhône-Ventoux, France, water
board) described by figure 34.
Figure 34. Schematic diagram of the Sorgues DWTP (Vaucluse, France) – Biological
manganese removal. Capacity: 28,800m3 · j–1
Another example, constructed in Canada, is shown in photo 20.
Photo 20. Biological manganese removal. View of Mangazur reactors – Woodstock

DWTP (Canada). Capacity: 6,600 m3 · j–1
Bacteria involved in biological manganese removal grow far more slowly than iron
3 months of natural seeding (in fact, that is why the feasibility of this type of process
was noticed late when analysing existing plant operation).
This period can be shortened by using sand that has been previously colonised by
bacteria from a similar plant.
water containing iron and manganese
When water contains both iron and manganese, there is a need to satisfy different
Redox potential conditions in order to oxidise both of these elements biologically (figure
28). Additionally, manganese removal can only commence when the iron has been
completely removed. In very rare cases, these elements can be seen to be removed
simultaneously by the same filter but only when the raw water properties are very
favourable and in exchange for a restricted velocity; this applies to the Poncey gravity
plant near Dijon, France (photo 21) that processes a nominal flow rate of 3,000 m3·h–1
using controlled aeration and filtration over a single, six sand filter stage, at an average
rate of 15 m · h–1 and a peak rate of 19 m · h–1, based on the following raw water
properties:
Iron = 0.2 to 1 mg · L–1;

Manganese = 0.2 to 0.5 mg · L–1;
pH = 7 to 7.2;
NH4 =Traces amounts to 0.1 mg · L–1.
Photo 21. Simultaneous iron and manganese removal followed by activated carbon.
Poncey gravity flow DWTP (Dijon, France) – Capacity: 72,000 m3 · j –1
This solution could only be implemented after an extended trial campaign on a pilot
plant (over 6 months). In most other cases, the following scheme is applied, based on
two successive filtration stages:
first aeration stage, set for biological iron removal;

first filtration stage (biological iron removal);
second aeration stage and/or raising of the pH (depending on the raw water
properties and first stage settings);
second filtration stage (biological manganese removal).
Depending on local conditions, the plant may comprise:
two pressurised stages (please refer to photo 21 for an example);

two gravity stages (large plants), vertically offset to allow the water to flow from the
first to the second stage;
a combined solution like the one for the Mommenhein (France) plant, outlined in
occured very quickly, allowing the second stage filtration cycles to be extended from
(operation in biological mode).
Despite the frequent need to resort to 2-stage filtration when water contains both Fe
and Mn, the biological solution is, generally, more cost-effective than the physical-
chemical alternative and always easier to use. On the other hand, although biological
iron removal has been thoroughly mastered (a good analysis will result in a secure
project), because of the high pH and especially the EH requirements, biological
manganese removal is subject to interference (NH4, H2S, OM, low pHS water…):
consequently, it is often advisable to carry out preliminary pilot trials.
Figure 35. Schematic diagram of the Mommenheim DWTP for the Hochfelden water
board (Lower Rhine, France). Capacity: 500 m3· h–1 capable of extension to 650
m3·h–1. Biological iron and manganese removal
Photo 22. Biological iron and manganese removal via two pressurised stages. Basse
Moder water board (France). Capacity: 1,400 m3 · j–1
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Specifics Water treatment manganese removal - Degremont® Page 1 of 13

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physical-chemical removal of manganese

Figure 30. Manganese stability diagram

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oxidation using oxygen

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Figure 31. Mn2+ removal by oxygenation

oxidation using MnO2

In such cases, the MnO2 needs to be regenerated at regular intervals using

The overall balance for reactions (1) and (2) will be :

degremont® water handbook

In practice, instead of ‘manganising’ sand, it is advisable to use a filtering medium

oxidation using chlorine

oxidation using chlorine dioxide

As already reviewed in the section oxidation and reduction (/water-and-

oxidation using potassium permanganate

Oxidation-reduction occurs between manganous manganese and permanganate

The theoretical proportion is 1.9 g of KmnO4 to 1 g of Mn. However, in practice, the

degremont® water handbook

to oxidise 1 g of Mn2+,0.9 g of ozone is required . The amount of ozone injected must

The Jonchay DWTP (France) is based on this principle (figure 33).

When manganese is complexed with OM and requires comprehensive clarification

biological removal of manganese – the Mangazur process

advantages of biological manganese removal

to use an oxidant, usually potassium permanganate, when starting up.

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Another example, constructed in Canada, is shown in photo 20.

Photo 20. Biological manganese removal. View of Mangazur reactors – Woodstock

water containing iron and manganese

Iron = 0.2 to 1 mg · L–1;

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first aeration stage, set for biological iron removal;

Depending on local conditions, the plant may comprise:

two pressurised stages (please refer to photo 21 for an example);

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< Iron removal (/processes-and- eliminating ammonium > (/processes-

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