OXYGEN SCAVENGERS

Purpose: To chemically remove the dissolved oxygen left in the feed water after the
feed water has been mechanically deareated.

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Oxygen that is dissolved in the feed water will cause the steel in the boiler and the feed water system to
be attacked by the water in a manner described as "pitting". The pits that are produced (they can vary
from tiny depressions to holes large enough to penetrate the boiler metal) are usually covered with
tubercles of iron oxide. Once pitting starts, it may be extremely hard to arrest. Pitting can proceed at a
surprisingly rapid rate and can occur not only in the boiler proper, but also in pre-boiler equipment
such as economizers, feed water heaters, and feed water lines.

This is an electrochemical reaction, where the metal surface exposed to the active oxygen is dissolved.
The metal surface is usually iron – the boiler.

The reaction is one where the iron is oxidized at the anode and released into the water. The electrons
from oxidation are then released and then absorbed by oxygen at the cathode. The reaction is:

Anode: Fe° → Fe ++ + + 2e -
Cathode: ½ O2 + H2O + 2e -- → 2OH-
Electrochemical Reaction: Fe° + ½ O2 + H2O → Fe(OH)2

As this reaction continues, due to the presence of free oxygen, a corrosion cell is formed which
eventually forms the classic oxygen pit.

On the other hand, where an oxygen scavenger is properly used in the system to eliminate fee reactive
oxygen, and where elevated temperatures exist, the Ferrous Hydroxide [Fe(OH2)] is converted to a
dense protective film referred to as magnetite (Fe3O4). This magnetite forms a protective film on the
reactive surfaces, protecting the metal from attack from water and oxygen. The reaction is:
Fe(OH2) → Fe 3O4 +H2 + 2H2O

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Once this film is formed, the scavenging of oxygen is important, because free oxygen can react to
revert the magnetite into iron oxide (hematite) which is porous.

2Fe 3O4 + ½ O2 → Fe 2O3 + H2O

With the reversion to iron oxide, you will see a reddish coating on the tubes and the returned potential
for oxygen pitting. Thus, it is very important that you scavenge the oxygen in the system at all times.

SODIUM SULFITE
Sodium Sulfite reacts chemically with dissolved oxygen, producing sodium sulfate. Since it is desirable
to remove dissolved oxygen from the feed water before it reaches a boiler, sodium sulfite is best
introduced continuously at some suitable point in the feed water system. An excellent application point
is the storage section of the feed water heater or deareator at a point six inches below the water line.

Chemical residual control is based on the maintenance of a specific excess of sodium sulfite in the
boiler water. The essential requirement being to maintain in the feed water at all times slightly more than
enough sodium sulfite to consume all of the dissolved oxygen that slips through the deaerating
equipment. When sodium sulfite is not fed continuously, protection of the boiler against oxygen attack
must depend on the reserve of sodium sulfite that is present in the boiler water. It is important that the
feed water and the boiler water are mixed thoroughly and as quickly as possible so that boiler water
sodium sulfite may consume feed water oxygen before the latter can cause damage to the boiler.

Sulfite as a treatment represents the second line of defense against oxygen corrosion. Primary
protection against this type of attack requires adequate facilities for mechanical deaeration of the feed
water plus a vigorous maintenance program to safe guard against oxygen leakage into the pre-boiler
system.

Sodium sulfate (the end product of the reaction between sodium sulfite and oxygen) is harmless in the
boiler water. Its presence will increase the boiler water solids if the sodium sulfite requirement is
comparatively high. Sodium sulfite concentrations more than the recommended maximum usage rate
are a waste of chemicals but will have no other undesirable effects in any but high pressure boilers.
Sodium sulfite tends to decompose around "hot spots" found in high-pressure boilers (<700 psig).

Uncatalyzed sodium sulfite can be fed by itself or along with other water conditioning chemicals.
Catalyzed sodium sulfite must be fed alone to protect the integrity of the catalyst.

The sulfite requirement is a rough indication of the amount of oxygen in the feedwater - approximately
eight pounds of sodium sulfite are required to consume one pound of dissolved oxygen.

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Rate of reaction between sodium sulfite and oxygen is quite rapid at temperatures near and above the
normal boiling point of water; at lower temperatures. When necessary, the speed of this reaction can
be accelerated considerably by using a trace amount of transition metal as a cobalt salt, blended into
the sodium sulfite. The Sodium Sulfite reactions are:

Uncatalyzed: 2Na 2SO3 + O2  2Na 2SO4

Catalyzed: O2 + 6CoSO4 + 2H2O  2Co 2(SO4)3 + 2Co(OH)2

Co2(SO4)3 + Co(OH)2 + Na2SO3  Na 2SO4 + 3CoSO4 + H20

Maximum and minimum limits are specified for control of boiler water sodium sulfite concentrations.
Do not hesitate to increase or decrease the feed of this chemical, as necessary, in order to keep boiler
water sulfite concentrations between the specified limits. Minimum residual levels of sodium sulfite
should be between 30 - 60 ppm, where the boiler is operating below 150 psi. The recommended limits
for sodium sulfite control are:

Boiler Pressure Sodium Sulfite Residual

0 – 150 psi 30 – 60 ppm
150 – 300 psi 20 – 40 ppm
300 – 600 psi 20 – 30 ppm
600 – 900 psi 10 – 15 ppm
900 – 1200 psi 5 – 10 ppm
1500 psi Sodium Sulfite Not Recommended

Catalyzed sodium sulfite (using cobalt sulfate) reacts far more rapidly than uncatalyzed sodium sulfite. It
must be fed by itself with a separate chemical feed system. Other boiler water chemicals are alkaline in
nature and when they are mixed with catalyzed sodium sulfite, the alkalinity reacts and causes the
cobalt sulfate catalyst to drop out. Catalyzed sodium sulfite should be fed through a stainless steel feed
quill into the storage section of the deareator approximately 6" below the operating water level of the
storage section.

The stoichiometry of the reaction shows that 7.88 ppm of sodium sulfite would be required to
combine with 1 ppm of oxygen. However, in the real world, the reaction is 10 ppm of sodium
sulfite are required to react with 1 ppm of oxygen.

(10 x Dissolved Oxygen) + Residual X 1.6 = ppm sodium sulfite required

Feed Water Cycles

HYDRAZINE
Hydrazine was the originally used as a substitute for sodium sulfite in high-pressure systems. It does
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not contribute solids to the boiler, which makes it very beneficial in high-pressure systems.
However, it is listed as a known carcinogen (OSHA PEL 0.1 ppm, subject to SARA Title III
Section 313 reporting) and as such requires special handling. Hydrazine has lost most of its market
and is now only used in a few large systems.

Hydrazine comes as a 35% liquid and is to be fed directly from the container into the feed water
system, at a rate of 0.05 – 0.10 ppm. The addition of Hydroquinone to hydrazine increases the
reaction time of the hydrazine from 10 – 100 times. The Hydrazine reaction is one f the slowest of
the oxygen scavengers where it is not catalyzed and the water temperature is below 300° F.

In temperatures above 750° F Hydrazine begins to break don into ammonia which becomes
corrosive to yellow metals.

HYDROQUINONE (C6H4(OH)2) HQ
Hydroquinone is usually used as a catalyst for Hydrazine, DEHA, and Carbohydrazide. It is
capable of acting as a stand alone oxygen scavenger.

Hydroquinone has very rapid reaction rate, even in relatively cold water. This ability enhances the
performance of the products that it is used as a catalyst in and allows it to perform in low-pressure
systems.

When using a mixed bed demineralizer, the rapid reduction reaction of this product will cause the
resin to turn black. This can become a problem during regeneration where the ability to visually see
the separation of the resin is important.

Hydroquinone is stable up to 572° F were it begins to break down. The final decomposition of this
material is into carbon dioxide. Hydroquinone is fed at a rate of 6.9 ppm of Hydroquinone to 1
ppm of Oxygen.

CARBOHYDRAZIDE (N2H3)2CO - CHZ

This is the first hydrazine substitute designed to provide a product that acts like hydrazine but does not
have the hazards contributed to hydrazine. The product is has a patent (#4,269,717) for use as an
oxygen scavenger. CHZ does not contribute to the boiler solids and reacts at a rate of 1.4 ppm of
CHZ for every 1 ppm of oxygen. This however will also form an additional 0.7 ppm of CO2, which will
have to be taken into account when calculating the neutralizing amine requirement. The material is
usually sold as a 6.5% solution and is fed to the feed water system to be controlled at 0.05 to 0.3 ppm
as Hydrazine. CHZ will decompose along the same lines as Hydrazine.
N,N-DIETHYLHYDROXYLAMINE (CH3CH2)2NOH) - DEHA
DEHA is a volatile oxygen scavenger, which is usually sold as an 85% or 25% liquid. It has the
ability to passivate the metal surfaces in the boiler, then pass out of the boiler with the steam, and
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act as a metal passivating agent in the return line system. The material was under a use patent by
Dearborn, which has run out.

DEHA can be catalyzed with either a copper salt or Hydroquinone. The feed rate of the DEHA s
1.24 ppm of DEHA for 1 ppm of oxygen, however it has been found that the best results are
found with a feed rate of 3 ppm of DEHA for every 1 ppm of oxygen.

In the boiler, the DEHA reaction also forms acetic acid to some degree. This is neutralized to
acetate in the boiler and then eventually breaks down into carbon dioxide. This must be taken into
account when reviewing the neutralizing amine program. You will also find some decomposition of
the DEHA into ammonia, however this does not occur until you have reached 534° F as compared
to the Hydrazine break down to ammonia, which starts at 334° F.

DEHA is a strong reducing agent that is capable of reverting reddish ferric oxide into magnetite in
the boiler. Concentrations of 150 – 300 ppb have proven to be effective to protect boiler metal
surfaces from corrosion.

DEHA can be tested for using DEHA test kits provided by major test supply companies. The test
is an iron test as DEHA reacts with ferric iron to form ferrous iron. Residual can be controlled
between 0.5 – 1.0 ppm.

METHYLETHYLKETOXIME (CH3CNOCH2CH3) - MEKO

MEKO is a volatile oxygen scavenger, which has a higher distribution ratio than DEHA. This
allows it to operate more effectively in long run condensate systems than DEHA. The distribution
ratio for MEKO is between DEAE and Cyclohexylamine.

MEKO has the fastest reaction time of any sodium sulfite substitute. It is fed neat from a 100%
solution to the feed water system at a rate of 5.4 ppm of MEKO for every 1 ppm of oxygen. The
control of the product is then 0.8 – 1.2 ppm in the system using an iron reduction test. MEKO
does not have passivation capabilities as DEHA, so it is not recommended for use in lay up.

ERYTHORBIC ACID (ERYTHROBATE) (C6H8O6) - EA

EA is an organic acid, which is an isomer of Vitamin C. This gives the product a GRAS status for
applications where the boiler water may come into contact with food production.
The pH of a 10% solution of EA is 2.1. The product is then buffered up to a pH of 5.5 with either
neutralizing amines or ammonia.
EA is catalyzed with transition metals as sodium sulfite, however if you have 1 ppb of iron in the
feed water, it will be sufficient to act as the catalyst. Copper is the most effective catalyst and is
added at a rate of 1 ppm of copper sulfate for every 50 parts of sodium erythorbate.

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The feed rate of 10% EA is 11 ppm of EA for every 1 ppm of oxygen. This is 1.1 times the feed
rate of sodium sulfite

EA is a very strong passivating agent for iron. It can assist in the formation of passive magnetite. It is
believed that break down products from the EA sequester iron and then assist in the formation of
magnetite on the metal surface.