How DMI 65 Granular Catalytic Material Works

Water Treatment
16 November 2010
Gheorghe Duta
Chief Engineer Technology and Development
Introduction
The purpose of this paper is to provide users of DMI 65, catalytic material with qualitative
information about how the material works, its capabilities and limitations and enable them
to apply the material to water treatment processes, in appropriate manner and with
confidence. The paper avoids the detailed complexity of solid surface electrochemical layers
and colloidal science, quantitative physical and chemical processes and reactions. For
readers having already significant knowledge in this area the paper brings more
understanding of what DMI 65 is and its intended use. Newcomers to this area are provided
with the bases, and perhaps motivation, for directing their more in depth studies as they
might wish.

Background information
DMI 65 is a granular catalytic material boosting oxidation processes in aqueous solutions
(water). The material is part of the broad category of products deriving their physical and
chemical action from the interaction of their metal oxide surface with the water molecules
and ions in solution.
In terms of solid surface interaction with water we distinguish the term adsorption as
attraction - interaction at solid surface level and absorption as transport and retention of
target ions through fine porosity inside the bulk of the material. Interaction of DMI 65 with
water molecules and ions in solution is initiated through adsorption.
Non catalytic type adsorbent materials retain target ions from water until sites available for
adsorption reach a maximum density, saturation, and concentration of target ions in the
treated water attain maximum acceptable concentration. At this point, the adsorbent
material has to be regenerated, to remove or replace the contaminant ions, or the used
material is disposed and new material loaded in the treatment container. When the process
works by swapping one type of ion for target ions from water the process is called ion

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exchange. It is appropriate to state that this category of adsorbent and some partly
absorbent materials remove the target ions from water. Obviously, the larger the surface
per volume of material the larger the amount of contaminant target ions which could be
retained. Purely catalytic materials adsorb the reactant ions from solution bringing them in
the proximity of chemical bonding. Then the reaction product moves away from the surface
of catalyst. Strictly speaking catalysts facilitate chemical reactions; they do not implicitly
remove anything. If the reaction product is a solid precipitate, often the product is retained
in the catalytic bed, hence removed by mechanical filtration. Many materials act in a mixed
mode; both ion exchange and catalytic action taking place. For those materials used
primarily for their catalytic action, ion exchange and dissolution of catalytic layer leads to
periodic regeneration or reactivation to correct the matrix of ions at their active surface.
Metals in water may be oxidised, oxidation meaning that the metal loses or shares electrons
with another element. Reduction of a metal ion means that the metal atom acquires one or
more electrons. Reduction and precipitation of metallic elements are usually conducted
outside the scope of water treatment applications.
The activity of hydrogen H+ or hydronium, H3O+ ions, the pH has a strong impact on the
reactions in aqueous solutions. At pH = 7 water is understood to be neutral. At lower pH
water is acidic. Adding a base increases the hydroxide, OH- concentration and the pH, and
water with pH greater than 7 is alkaline.

DMI 65 Catalytic material

DMI 65 is a granular material of dark brown to black colour. This colour is given by the
manganese oxide in the outer layers of the granules. DMI 65 is a catalytic material in the
true meaning of the word. DMI 65 facilitates or enhances oxidation and does not get
consumed in the reactions. The material does not need regeneration or reactivation and
does not display a decaying capacity to do its catalytic work. Replacement is thought well
before degradation of catalytic capacity takes place. Over 5 to 10 years period, through
many backwashing operations of the bed to remove retained solids, the catalytic layer is
degraded by contact between particles and mechanical abrasion. Then the material has to
be replaced.

Iron, Fe precipitation and removal using DMI 65

The key application of DMI 65 in water treatment is for oxidation, precipitation and removal
of manganese, Mn. Catalytic surface of DMI 65 contains manganese oxide or exposes
manganese and oxygen sites for adsorption of ions in the water. High performance in
oxidation and precipitation of iron, Fe comes in part from the fact that atomic radii of the
two elements, Fe and Mn are almost equal; 127 pm (picometer) for Mn, and 126 pm for Fe.
We discuss first the application of DMI 65 for Fe oxidation and removal because Fe is a more

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common contaminant in water than Mn and a number of other metals could be oxidised
and precipitated as metal oxy-hydroxides, whereas manganese is a rather special case.

O
O

O
O

O
O

H
O

OH

OH
OH

Fe

OH
Fe

Fe adsorption
OH
H

OH
Fe

O
M

OH

OH
Fe

OH

O
O

Ferric hydroxide

Metal oxide catalyst

Iron oxidation at catalytic surface.

In the above figure the catalytic surface is presented in a simplified smooth form. Letter M
was used to represent a generic metal ion in the lattice of the surface. Letter O, in the
centre of circles, represents an oxygen atom. Various ion size and oxygen molecule (blue)
are represented at true relative scale. Except the oxygen molecule, bonded irons are shown
as tangent circles. The interpretation for letters and ions in the figure Ion oxidation at
catalytic surface is:
M: generic metal ion in the catalytic surface lattice (Mn+); n = 1, 2
O: oxygen atom or ion (O-)
Fe: iron atom or ion (Fe2+, Fe3+)
H: hydrogen atom or ion (H+)
OH: hydroxide, or hydroxyl anion (OH-)
H2O, water molecule shown as tangent circles
Fe (OH)2, ferrous hydroxide is shown as tangent circles
Fe (OH)3, ferric hydroxide, shown as tangent circles, brown colour
O2, oxygen molecule, atoms shown at covalent bonding distance, blue colour

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Water molecules are an electric dipole and they could be attracted to the ion sites on the
catalytic surface. The following process is called hydroxylation of metal oxide surface. The
oxygen end of the water molecule is first attracted to the metal in the lattice. Subsequently,
oxygen in the neighbouring site attracts the hydrogen and cause splitting of the water
molecule into hydroxide OH- and hydrogen ion H+. This is a dynamic process, not taking
place simultaneously at all sites of the catalyst. Side sliding of the attached matrix of
hydroxide and hydrogen ions, release from adsorption and recombination take place at the
same time.
Dissolved ferrous hydroxide is attracted with the Fe end towards the lattice oxygen of the
catalytic material. This brings the Fe in the proximity of covalent bonding with the hydroxide
ion of a neighbouring site and ferrous hydroxide changes into ferric hydroxide. Electric
charges are better balanced in the ferric hydroxide and the ferric hydroxide could move
easier away from catalyst surface. Moreover, ferric hydroxide is insoluble and precipitates in
crystalline form aggregates of size from 3 nanometre and larger. The aggregates coagulate
in larger flocks and are retained in the catalytic bed.
While ferrous hydroxide is converted into ferric hydroxide, the concentration of ferrous
hydroxide at the catalytic surface decreases. In the bulk of the water, away from catalytic
surface, the concentration of ferrous hydroxide is higher and ferrous hydroxide diffuses
towards the lower concentration according to diffusion law. Diffusion flux is linearly
dependent with concentration gradient over distance.
Dissolved oxygen contributes to production of hydroxide ions through direct oxidation of
hydrogen in combination with Fe splitting the water molecule and by reacting with the
hydrogen at the catalytic surface.
Very important to note is that although a source of oxygen is needed, oxidation and
precipitation of Fe is driven by hydroxide ion. The consequences are that even under
relatively acidic conditions hydroxide ions (very strong anion) are easier available for binding
to Fe than oxygen. Thus, Fe is not very difficult to oxidise and precipitate around neutral pH
condition. In addition, concentration of hydroxyl ions increases with pH value exponentially
and so does the rate of oxidation and precipitation of Fe.

Manganese, Mn precipitation and removal using DMI 65

DMI 65 is a catalytic material specifically tailored to the oxidation and removal of
manganese. The catalytic surface contains manganese oxide for brining into proximity of
covalent bonding manganese and oxygen atoms from water. However, oxidation and
removal of manganese, Mn is vastly different from that of Fe. A major difference is caused
by solubility of manganese hydroxide, Mn (OH)2. Manganese does not precipitate as oxyhydroxide but as oxide, MnO2 and higher valency oxides. Presence and concentration of
hydroxide anions does not help much in the precipitation and removal of manganese.
Strong oxidative conditions and oxygen source is needed. To oxidise manganese a strong

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source of highly reactive oxygen such as ozone is a possible solution and often used. In the
case of DMI 65 dissolved oxygen level has to be maintained high. Manganese hydroxide will
be attracted with the manganese end to the lattice oxygen. Oxygen molecule has to be
available in the proximity for facilitating oxidation through the oxygen from lattice and
swapping to the lattice with molecular oxygen. Conditions for this to happen are statistically
less probable and reaction is of much slower rate than the oxidation of Fe via hydroxide.

O
O

O
O

O
O

H
O

OH

OH
O

Mn

O
Mn

Mn adsorption
OH
H

OH
Mn

O
M

OH

OH
Mn

Manganese
Oxide

O
O

Metal oxide catalyst

Manganese oxidation at catalytic surface.
While increase in pH facilitates oxidation and removal of manganese, under anoxic
conditions, although pH could be alkaline, manganese could dissolve back into the water
and also could be mobilised into water from the catalytic surface. Consequently, regardless
of the target contaminant to be removed, anoxic conditions have always to be avoided to
protect the catalytic layer against leaching into water. When oxidising manganese the
recommended pH is close to 8.
Presence of Fe and its oxidation and removal facilitates the removal of manganese.
Similarity of atomic radius facilitates co-precipitation of manganese with Fe as manganese
ion. Backwash sludge formed this way is less stable in the environment because the high
sensitivity of manganese to move in solution.
Manganese oxide has good autocatalytic effect. When backwashing it is better to stop the
process before the water becomes very clear. Manganese oxide residue in the filter bed will
enhance manganese oxidation.

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Role of sodium hypochlorite, NaOCl

Catalytic surface has to be maintained clean so that ions in water could come in contact
with it. Sodium hypochlorite is injected to prevent bacteria growth and blinding with slime
of catalytic surface. At the same time NaOCl is a source of oxygen more reactive than
molecular. Ideal residual to be maintained downstream of catalytic filter is 0.2 mg/l (0.1 to
0.3) free chlorine. Higher residual of free chlorine and therefore higher sodium hypochlorite
level in the catalytic filter does not always help. It could have an adverse effect due to
venting of chlorine and increase of competing sodium ions, Na+.

Why remove Fe and Mn from water

In the case of drinking water limits maximum contaminant limit for Fe and Mn is limited on
aesthetic considerations. The limits vary from country to country, although is known and
accepted that Fe in excess of 0.3 mg/l and Mn in excess of 0.1 mg/l cause staining of laundry
and plumbing fittings. Fe and Mn are essential elements and deficiency in our diet could
cause serious health problems. Health problems could be caused also by excess of the two
elements in our diet. In terms of limits for public health the limits were unfortunately
established based on adult body weight and water consumption, and it was incorrectly
assumed that children fit the same rules and are ok. Children have higher permeability of
organ and cell membranes and drink about 5 times more water per kilogram of body weight
than adults. Rather, a common sense point, the two elements being essential to our health,
before establishing health limits to include children, we should have looked at the Fe and
Mn content of human breast milk. The Fe content in human breast milk is 0.3 mg/l and Mn
varies across world population from 0.003 to 0.010 mg/l. We could guess that limits in
drinking water a lot higher than in human breast milk could damage the health of children.
By chance in the case of Fe we got things right. In the last few decades, evidence beyond
any doubt has been accumulated that Mn is neurotoxic to children at much lower
concentration than thought before. Mn accumulates in the brain and the strongest
measurable effect is poor memory. The limit set by US EPA of 0.05 mg/l seems acceptable
and should not be exceeded.
In the case of discharge of treated water into aquatic environments, typically concentration
background level should not be exceeded by more than 10%. Local EPA sets the rules.
Aerobic aquatic fauna takes up oxygen from water through membranes exposing an alkaline
protective layer in contact with the water. This is the case of gills and skin. Dissolved Fe and
Mn coming in contact with the respiratory membranes could oxidise and precipitate.
Presence of precipitated Fe and Mn leads to local generation of highly reactive species and
burning of the tissue around. Bleeding of gills, asphyxiation, red fungus attack and other
diseases are the result of excessive dissolved Fe and Mn. Fe is more reactive and dangerous
than Mn.

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DMI 65 operating conditions of concern

Treatment processes have to be conducted in such manner so that the catalytic surface of
the material is kept clean and available to ion from water to contact.
Water with large amount of suspended solids has to be clarified before passing it through
the catalytic filter with DMI 65. Acceptable level of suspended solids depends on their
nature. Larger amount of mineral suspended solids then organic suspended solids could be
handled.
Bacteria could grow and deposit slime on DMI 65. Thus disinfectant and oxidation
conditions have to be maintained.
Water containing clays and large organic molecules may result in deposition of such
material on the surface of DMI 65 and blinding of catalytic surface. Treatment for removal
of such contaminant before the catalytic filter is needed.
Polymer flocculent could also stick to the DMI 65 and blind catalytic surface.
Hard, unstable groundwater could cause scale deposition in the catalytic filter and bind the
material in a solid mono bloc. In such case the DMI 65 material in the bed is lost; has to be
replaced. Treatment for stabilizing the water to prevent scale formation in the catalytic filter
has to be carried out.
Both low acidic pH and anoxic conditions could cause dissolution of manganese from
catalytic layer of DMI 65 and loss of its capacity. Excessively high pH means excessive
concentration of hydroxyl ions (corrosive to metals) and could also cause dissolution of
manganese from the catalytic layer.
Do not use demineralized water, distilled water or water known to be strongly corrosive to
metals for initial soaking and activation of DMI 65.

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