DIETHYL HYDROXYLAMINE AS OXYGEN SCAVANGER FOR

BOILER WATER TREATMENT

ANIL KHERA, N. ANBANANTHAN

Ion Exchange India Ltd

19/A, Phase II, Industrial Development Area,
Patancheru 502 319, Medak Dist, AP, India.

Waterside corrosion is a major problem in steam generation systems causing

damage, inconvenience, down time, replacements and cosequent financial
losses every year. The corrosion can take place in pre-boiler, feed water
systems, boiler drums & tubes and post boiler system comprising of steam
and condensate equipments piping. The cause for corrosion is primarily due
to the presence of dissolved oxygen and carbondioxide. The presence of
dissolved oxygen is found as key cause of feed water, boiler water and even
condensate corrosion in boiler system whereas carbon dioxide is known to
cause corrosion in return line condensate system.

Oxygen corrosion occurs through an electrolytic process using the boiler

system metal as current path and boiler water as an electrolyte. To control
the corrosion due to oxygen, the feed water should be free of oxygen.
Various methodologies were adopted to remove the dissolved oxygen. The
dissolved oxygen in the feed water is partially removed by thermal
deaeration. The removal of dissolved oxygen is not complete in this process
and the residual dissolved oxygen is normally about 0.007 ppm. This low
concentration can influence the corrosion. The residual dissolved in water
oxygen can be removed by using oxygen scavengers.

Corrosion by oxygen in the boiler can be controlled by the addition of an

“oxygen scavenger” to the preboiler section of the steam generating system.
One of the oldest oxygen scavenger is sodium sulphite. In 1920, sodium
sulphite was first used as an oxygen scavenger. Later, hydrazine was first
introduced in Germany in early forties. Due to the introduction of high
pressure boilers, the demand for the use of hydrazine increased compared to
sodium sulphite. Hydrazine is technically superior when compared to sodium
sulphite especially in high pressure boilers. In addition to its oxygen
scavenging capabilities, hydrazine could able to passivate ferrous metallurgy
present in the boiler.

In early seventies, hydrazine was identified as a toxic substance and

suspected carcnogen. With hightened sensitivity toward employee’s health
and safety, the water treatment industry directed their efforts towards the
development of alternative oxygen scavanger. Many alternative oxygen
scavangers were developed. These include catalysed diethylhydroxylamine
(DEHA), carbohydrazide, methyl ethyl ketoxime (MEKO), hydroquinone,
erythorbic acid etc. The catalysed oxygen scavenger –
DIETHYLHYROXYLEAMINE (DEHA) was first introduced in India by Ion
Exchange India.

Properties of DEHA

DEHA is a colourless to pale yellow transparent liquid. It is the derivative of

hydroxyl amine. It is freely soluble in water. Chemically it is a reducing agent
and hence it oxidizes. It reduces ferric ion and converts into ferrous ion.
Thermally in presence of water, it decomposes . The details of the above
chemical properties with reference to high temperature systems are
discussed here.

Oxidation of DEHA

DEHA reacts with dissolved oxygen leaving to harmless byproducts. The

overall reaction of DEHA with dissolved oxygen can be summarized as here
below:

4 (CH3CH2) 2 NOH + 9O2 CH3COOH + 2N2 + 6 H2O

According to above equation 1.24 g of DEHA is required to remove 1 g of

dissolved oxygen. However, in practice, it has been observed that about 4-
ppm of DEHA is required. It is, therefore, probable that the reaction does not
follow the above direct path but involves various intermediate steps. Various
mechanisms are available for such high consumption of DEHA in the
literature.

Acetic acid is one of the major decomposition of DEHA. The acetic acid
formed due to the decomposition of DEHA is retained by hydroxide alkalinity
in boiler and is not found in steam. It gets converts into acetate salt and
under most boiler conditions presence of it does not create any problems.
However, in systems operated without hydroxide alkalinity, small portions of
acetic acid at ppb level were observed. Such situations apply to high-
pressure boilers where all volatile treatments are used. As the level of
dissolved oxygen after deaerator is so small, the acetic acid level will also be
correspondingly very low indeed. However, the presence of acetic acid does
not mean that it is only originated from DEHA. Instances were reported
especially in nuclear power plants that the acetic acid could also be formed
due to the presence of organics in the feed water.

Apart from acetic acid nitrites, nitrates and acetaldehyde are also reported to
be formed due to DEHA oxidation. Table 1 summarizes the various
byproducts formed due to DEHA oxidation and their implications. Table 1
depicts the details of nitrites, nitrates and acetaldehyde.

OXIDATION PRODUCTS Details

Nitrites and nitrates Fund only in boiler. Nitrite is found below 1000
psig and concentration of nitrite found is very
low. Levels are insignificant for boiler operation.
Acetaldehyde Is found almost entirely in steam due to low
boiling point (21 deg c at atmospheric pressure).
Its toxicity is low and do not pose any major
problem in boiler operation.

Reduction of ferric ion

As iron is exposed to an aqueous environment, it begins to corrode leading to
formation of rust Fe2O3 (Hematite). The iron in haematite is found in Fe 3+
form. DEHA reduces Fe3+ to Fe2+. The partial reduction of Fe3+ to Fe2+ leads
to the formation of magnetite, Fe3O4. The magnetite layer act as a passive
layer and thus provides a protective barrier against the corrosive attack.

Thermal decomposition of DEHA

DEHA is thermally stable up 300 psig and some breakdown occurs at 1000
psig. The major thermal decomposition products appear to be diethylamine
or ethylmethylamine. It further decomposes to ammonia. But the quantities
of ammonia formation are insignificant under most operating conditions. It is
to be noted that the decomposition of DEHA initiates from 540 F only.

The byproducts of DEHA, amines are helpful in raising pH of condensates.

This reduces the consumption of neutralizing amines. The formation of
ammonia is very low and hence threat to yellow metallurgy in the system is
very minimum when compared to hydrazine based treatment.
Advantages of DEHA over sulfite and hydrazine

Reaction kinetics

The reaction rate of reaction with dissolved oxygen depends upon pH,
temperature and concentration of both DEHA and dissolved oxygen itself.
Figure 1 depicts the sulfite reacts faster than hydrazine and DEHA at 21°C
and pH 8.5 whereas DEHA reacts faster than Hydrazine. DEHA takes the
second position in the spectrum. However, considering the high pressure
operation, DEHA takes the first position. Moreover, when DEHA is catalyzed,
the activity could be enhanced.
 AFTER 30 MIN AFTER 15 MIN
100

90
80
70
60

50
40
30

20
10

0
SULFITE DEHA ERYTHORBIC ACID HYDRAZINE CARBOHYDRAZIDE
Figure 1 : Percent oxygen reduction of oxygen scavanger at 21 °Cand pH 8.5

The catalyzed DEHA is nearly as fast as catalysed sulfite and much better
than catalysed Hydrazine when tested at 21°C Fig II shows the efficiencies
of common oxygen scavengers at 21°C. The catalyzed DEHA performs equal
to catalyzed sulphite. This shows that the DEHA based formulation
performance exceeds all other common oxygen scavengers used in boiler
water treatment.

120

100

80

60

40

20

0
CAT.SULFITE DEHA.CAT ERYTHORBICACID CAT.HYDRAZINE CARBOHYDRAZIDE

Fig2: Oxygendeficientefficiencies ofoxygenscavangers

Metal passivation

Sodium sulfite hardly has ability to reduce ferric ion to ferrous ion at low
concentrations. The studies indicate that even hydroquinone and
carbydhydrzide do not enhance pasivation. The role of DEHA as a reducing
agent was discussed in earlier proves its efficiency. Hydrazine also behaves
like DEHA on iron reduction. As hydrazine residuals are not present in
condensate, the protection of iron metallurgy in the condensate area is
seldom possible. In such instances, DEHA scores additional benefits over
hydrazine.

Total dissolved solids

The total dissolved solids build up in the boiler water one of the primary
disadvantages exists for sodium sulfite based treatment. Hydrazine and
DEHA do not impart any dissolve solids build up in the boiler water.

Thermal decomposition byproducts

The oxidation product of sulfite and TDS in boiler water. The decomposition
of sulfite has been observed at higher temperatures above 540 Deg F (950
psig). The decomposition products are usually sulpher dioxide and sodium
sulphate which may lead to corrosive attack. The hydrazine decomposes to
ammonia at 350F. This is corrosive to copper and its alloys. However, the
corrosion is proportional to the ammonia concentration. Fig.3., compares
the generation of ammonia in hydrazine and DEHA based steam generation
system. The thermal degradation products of DEHA were discussed earlier
and they do not have any significant impact on the corrosion of boiler
metallurgy. Therefore, the use of DEHA provides additional benefit over
sulfite and hydrazine.
 PPMNH3 GENERATED PER PPMPRODUCT 1
0.9
0.8
0.7 HYDRAZINE
0.6 DEHA
0.5
0.4
0.3
0.2
0.1
0
200 340 440 560
TEMPERATURE in F

Figure :3 : Ammonia formation due to hydrazine and DEHA decompositon

Volatility

DEHA is highly volatile. This property provides additional advantage over

sulfite and hydrazine. It is travels with steam and reacts with dissolved
oxygen, which often gets reingressed in steam and condensate system.
DEHA residuals in steam passivate condensate lines whereas Hydrazine does
not volatilise and reach such systems. The volatility of DEHA increases from
100 psig to 300 psig and then falls gradually at increasing pressures. DEHA,
therefore, behaves in a similar manner as neutralizing amines. It would,
therefore, be expected that volatility at high pressure will still be for giving
residuals in steam.

Toxicity

The LD 50 value (rats, oral) of DEHA is >2000 mg/kg as against 50 mg/kg of

hydrazine. This shows that the toxicity of DEHA is very low when compared
to hydrazine.
The above comparisons confidently vouch for the superior performance of
DEHA over hydrazine and sulphite which are well proven oxygen scavengers
in steam generation systems. In addition to the above data, a few the case
studies are summarized here below to reiterate the importance of DEHA.

Case history 1

A large paper mill operated with the following conditions. The co-ordinated
phosphate with a reserve of 10-15 ppm in boiler water. Hydrazine was used
as oxygen scavenger. Blend of neutralizing amines were used to prevent for
condensate corrosion was being practiced. They wanted to replace hydrazine
in view of its health hazards. The suggestion to use catalyzed DEHA was
accepted.

Steam Generation 3,50,000 1bs/Hr

Operating Pressure 900 psig
Superheated steam temp.
460 Deg C
after attemperation
Make up Water DM
Feed Water Deaerated
Condensate Recovery 50% (Not polished)
Cycles of Concentration 70

Initially 300 ppb of catalysed DEHA was used. Upon the use of DEHA the
demand for neutralizing amines was reduced from 3 ppm to 2 ppm. They also
monitor the levels of copper and iron. Results are reported in the following
table. The Cu and Fe levels reduced by a factor of 10 over one year.

A new economizer was installed but was kept in moist condition before use.
Therefore, it got corroded and the corrosion could be seen visually. The
cleaning was not possible and hence they stated using catalysed DEHA with
out cleaning. After a few months of use the economizer was found to be very
clean. This indicates the reduction capability of DEHA to convert ferric to
ferrous ions. Thus it passivates the system and control further corrosion.
Case history 2

An utility plant operated at following conditions used DEHA instead of

hydrazine. The steam generation was 8,50,000 1bs for average of 10hrs per
day. It was operated at 850 psig. Regular monitoring systems were installed
by the customer. Initially, the dissolved oxygen concentrations were
measured and compared with their old data on hydrazine. The following table
compares the measured dissolved oxygen values for hydrazine and catalyzed
DEHA usage.

After Deaerator Feed Water Condensate

With Hydrazine 7 ppb 5 ppb 10 ppb

With Catalysed 6 ppb 5 ppb 4 ppb

The above table enunciates that dissolved oxygen level dropped down in
condensate when compared to hydrazine system. This indicates that DEHA
should present in the condensate line to reduce the oxygen concentration.
Therefore, the condensate was taken and analyzed for DEHA. The DEHA at
such low concentrations is difficult to analyze by normal methods. Therefore,
it is analyzed by indirect method. The method adopted was the reduction of
Fe3+ ion to Fe2+ and complex it with a complexing agent. The complexing
agent is 3-[2-Pyridyl]-5,6-diphenyl-1,2,4-triazine-4,4´-disulfonic acid.Na-salt).
It forms a purple colour complex with iron at very low concentration. The
analysis of DEHA in the condensate was proved its presence and the
performance it imparts on corrosion control till the condensate line is
established.

We addressed the properties of catalysed DEHA over other oxygen

scavengers normally used in industrial boilers. Many field trials support the
performance of DEHA in reduction of oxygen, reduced corrosion rate.
Although, the DEHA posses many advantages, one of the main disadvantage
is its cost. In addition to the cost of DEHA, the analysis of low concentration of
DEHA is also cost prohibitive. Presently, the availability of indigenous DEHA
test kit reduces the DEHA analysis cost significantly with out affecting its
analytical quality. Presently, many Indian industries hydrazine is still
popularly being used in medium and high-pressure boilers. Therefore, the
scope of the article is to create an awareness about the use of DEHA in place
of hydrazine.

About the authors…

Mr. Anil Khera is presently the head of specality chemicals operation of Ion
Exchange India Ltd. He has got over 20 years of experience in the field of
cooling and boiler water treatment. anil.khera@ionexchange.co.in

Dr. N. Anbananthan is presently the head of R&D team of Ion Exchange India
Ltd. n.anbananthan@ionexchange.co.in