A New Patented Oxygen Scavenger to Replace Hydrazine in Boiler Water

Treatment Applications
Junichi Takahashi*, KURITA WATER INDUSTRIES LTD., Tokyo, Japan
Dr. Hermann Kempen KURITA EUROPE GmbH, Viersen, Germany
Takatoshi Satou, KURITA WATER INDUSTRIES LTD., Tokyo, Japan
Yukimasa Shimura, KURITA WATER INDUSTRIES LTD., Tokyo, Japan

Abstract
Dissolved oxygen in feed water of boilers and other steam generating systems can cause serious
corrosion and deposition problems. The prevention of such problems is vital for the continuous and
trouble free steam production and for the integrity of the whole plant. Since the first report by
Zimmermann (ex: Zimmermann, 1948) chemical scavenging of remaining dissolved oxygen has been
widely accomplished by treating the water with hydrazine. However due to the known negative effect
of hydrazine on the human body, worker exposure to this compound is subjected to extremely severe
tolerances by government occupational health agencies (ex: Schabacher, 1982). A new type of
chemical oxygen scavenger has been developed which shows excellent oxygen reduction effect in a
wide variety of conditions and is able to replace hydrazine in boiler applications without showing the
typical disadvantages of other hydrazine replacement chemicals.

Keywords
Oxygen scavenger, hydrazine replacement, corrosion, boiler, steam production

Introduction
Dissolved oxygen in feed water contributes to corrosion in all parts of a boiler system, such as boiler
main body, heat exchanger and economizer arranged upstream as well as steam and condensate piping
arranged downstream of the boiler main body (ex: Uhlig, 1967; Jonas, 1990). Oxygen-promoted
corrosion is an electrochemical reaction showing increasing reaction rate with increasing temperature.
Even very low concentrations of oxygen is steam generating equipment can lead to severe problems,
especially because it can result in pitting attack on the metal surface. Furthermore oxygen has been
reported as a factor in flow accelerated corrosion (ex: Thompson, 1989).

To inhibit the corrosion in the boiler system, dissolved oxygen in feed water should be removed by
deoxidizing treatment of the feed water. Conventionally, a combination of chemical treatment and
physical treatment is applied for the removal of dissolved oxygen. The mechanical degasification is
typically carried out with vacuum degasifiers, which will reduce oxygen levels to less than 0.5 – 1.0
g/m3, or with heating type deaerators that will reduce the remaining dissolved oxygen concentration to
less than 0.01 g/m3 (ex: Jonas, 1987). As for the chemical treatment, a method of adding an oxygen
scavenger such as hydrazine, hydrazine derivatives (ex: Schneider et al., 1986), sodium sulfite,
hydroxylamine derivatives (ex Cuisia et al., 1993), ketoxime compounds (ex: Van der Wal, 1989) or
saccharides into the boiler feed water has been widely employed.

Hydrazine efficiently eliminates the residual oxygen in the water by reacting with oxygen to give
water and nitrogen. In addition it forms and maintains an adherent protective layer of magnetite on the
iron surface. However, while the safety for humans of hydrazine is doubtful and thus the handling of
hydrazine is a risk (ex: DHEW Publ. No. 78 –172, 1978), all other compounds to be applied as
suitable replacement for hydrazine show some disadvantages in their application and/or performance.

Sodium sulfite and saccarides are widely applied in steam generating systems in the food industry.
However being non-volatile compounds they concentrate as solid content in the boiler water
increasing the electrical conductivity and being unable to provide efficient protection against oxygen
based corrosion in the steam condensate system.
Among the alternative volatile oxygen scavengers the application of hydrazine derivatives like
carbohydrazide is not a fundamental solution, because under increased temperature conditions
hydrazine will be formed again, while other alternatives like oximes and hydroxylamine compounds
show disadvantages in their thermal stability and reaction speed.

Experimental Boiler Studies

Knowing about the disadvantages of existing volatile hydrazine replacements, an intensive
screening procedure for alternative chemical compounds to be applied as oxygen scavenger in
steam generating systems was carried out by using a natural circulation test boiler. The layout
of the system is shown in Figure 1.

T
Steam Condensate

Condenser
Chemical Depressor
Injection DO meter

Ｐ
Heater

Heating tube
Feedwater
Cooler
Blowdown Depressor

Chemical Analysis

Figure 1: Natural Circulation Test Boiler

The oxygen scavenging effect, thermal stability and volatility of potential oxygen scavenging
compounds have been evaluated by using this test boiler. During the screening procedure
heterocyclic compounds having N-substituted amino group were evaluated as being the most
effective candidates. Typical examples of this group are listed in Figure 2.

To evaluate the oxygen scavenging effect, ion exchange water saturated by oxygen in air at
60°C was fed to the test boiler. Tribasic sodium phosphate was added to the feedwater in an
amount of 1 mg/L. The boiler was operated at an internal temperature of 290°C, an
evaporation rate of 7.2 L/h and a blowdown rate of 0.8 L/h. Generated steam was condensed
completely and the concentration of dissolved oxygen in the condensate was measured using
a dissolved oxygen meter. Results for dissolved oxygen concentration in the condensate are
shown in Figure 3 against the dosage of the oxygen scavenger.
 N-aminomorpholine 1-amino-4-methylpiperazine (1A-4-MP) N-aminohexamethyleneimine

1-aminopyrrolidine (1AP) 1-aminopiperidine

Figure 2: Examples of tested N-amino substituted heterocyclic compounds

5
Pressure: 7.5 MPa
Concentration Cycle: 10
DO in condensate (mg/L)

4 Blowdown: 0.8 l/h

Phosphate (as PO 4): 10 ppm
Na/PO4 mol ratio: 3.0
3

DEHA
1
１AP
Hydrazine MEKO
MEKO
0
10 1A-4MP 15
1A-4-MP
0 5 20 25
Dosage in feedwater (mg/L)

Figure 3: Oxygen scavenging effect

In further tests the performance of the new volatile oxygen scavenging compounds has been
compared to hydrazine and other existing materials on the market. Test results for thermal
stability and volatility received for 1-amino-4-methylpiperazine (1A-4-MP) during the test
procedures are shown in Figure 4, 5 together with the results for hydrazine,
diethylhydroxylamine (DEHA) and methylketoxim (MEKO).
 100

1A-4-MP
80 MEKO
Residual content [%]

Hydrazine
60 DEHA

40

20

0
0 100 200 300
Temperature [°C]

Relatscavenging
Figure 3: Thermal stability of oxygen ive compounds
Volatility

100

DEHA
10
MEKO
Relative Volatility

1 1A-4-MP

0.1
Hydrazine

0.01
100 200 300
Temperature [°C]

Figure 4: Relative volatility of oxygen scavenging compounds

Furthermore the effect of the new volatile oxygen scavenger based on 1-amino-4-methylpiperazine
on pH and conductivity in high pressure boilers was investigated. The results showed that the effect on
pH and conductivity is hardly measurable at all.

The following test conditions were applied in the natural circulation test boiler (Fig. 1): Pressure was
set to 7.5 MPa and demineralized water was used as feedwater with dissolved oxygen concentration of
8 – 10µg/L. Cycles of concentration were established at 100 and condensate return rate was 90%.
Trisodiumphosphate (Na3PO4) was used as boiler compound and the effect of the new oxygen
scavenger on pH and conductivity was evaluated for different phosphate concentration levels in the
test boiler.
 10.4

10.2 Theoretical curve of Na3PO4

With new oxygen scavenger
10.0 Blank
Temperature

Relative
Volatilit
pH at 25°C

9.8
[°C]

9.6
y

9.4

9.2

9.0
1 2 3 4 5 10
PO43- (mg/l)

Figure 6: Effect of the new oxygen scavenger on boiler water pH

10

8 Theoretical curve of Na3PO4

Conductivity 25°C [mS/m]

with new oxygen scavenger

Blank
6

0
0 2 4 6 8 10
PO43- (mg/l)
pH at 25°C
Figure 7: Effect of the new oxygenTemperatu
scavenger on boiler water conductivity
re [°C]

Relaintivthe test boiler gave the same corrosion inhibition effect by

Corrosion tests using corrosion coupons
e
the new oxygen scavenger as was achieved by the application of hydrazine under the same conditions.
Visual inspection of the heating tubeVo latili showed for both products the same formation of a dense
surface
magnetite layer. The following test tconditions
y were used for the test: Test period = 168h; Pressure =
7.5 MPa; Concentration Cycle = 10; Blowdown = 0.8 l/h; Demineralized make-up water; DO in
feedwater = 15-30 µg/L, Boiler compound： Na3PO4
 Oxygen Scavenger Hydrazine 1-amino-4-
methylpiperazine

Appearance of
heating tube
(carbon steel)

Adhered iron on 1.2 µg/(cm2h) 1.2 µg/(cm2h)

heating tube
Corrosion rate 0.046 g/(m2h) 0.046 g/(m2h)
of test coupon
Fe in the blow-down 0.02 mg/L 0.02-0.03 mg/L
Figure 8: Corrosion test results
Test Boiler (SUS 304); Test Period = 72hr

Toxicological data
As the new product shall be applied as a save replacement for hydrazine in boiler treatment
applications, the toxicity data of the material is of great interest. Figure 8 shows an overview for
toxicological data of hydrazine and possible oxygen scavenger alternatives including 1-
aminopyrrolidine (1AP) and 1-amino-4-methylpiperazine (1A-4-MP).

Hydrazine Carbo- 1AP MEKO 1A-4-MP DEHA

hydrazide
LD 50 (mg/kg) 167
Mouse, oral 59 intra- 409 930 (rat) 1750 2190
abdominal
Micronucleus
test (mouse) Positive N.A. Negative N.A Negative N.A.

Environ. toxic.
7.3 mg/L N.A. 76 mg/L N.A. 1300 mg/L N.A.
LC50 (fish)
Remarks Carcinogen Generates
Carcinogen
for animal Hydrazine at -- -- --
150 °C for animal

High Toxicity Low

Figure 9: Toxicity Data

Field application
Since its introduction on the market in 1997, the new oxygen scavenger based on 1-aminopyrrolidine
has been applied to more than 200 customers. The new chemical based on 1-amino-4-
methylpiperazine was developed on 2002, and it has been applied in approximately 100 high and
medium pressure boiler systems up to now to replace hydrazine or other alternative oxygen scavengers.
1-amino-4-methylpiperazine has some advantages, milder smell (one fortieth milder with odor
threshold) and lower toxicity (Fig.9), over 1-aminopyrrolidine. In all cases the formation of the same
excellent magnetite layer that was observed during the experimental boiler studies, was also found in
the field applications and the results have been documented in several cases during shutdowns of the
treated boiler systems. One textile company, boiler pressure is 9.5 MPa, quitted using hydrazine and
changed it to the new oxygen scavenger based on 1-aminopyrrolidine on 1999 and alternated it to 1-
amino-4-methylpiperazine base one on 2003. Any problem concerning with water treatment has been
reported among non-hydrazine treatment, more than 6 years.

Proper control of the residual oxygen scavenger concentration in boiler and feedwater line is an
indispensable part of the boiler treatment program. The analysis should be possible on site and should
provide reliable results within a short time. The new oxygen scavenger based on 1-amino-4-
methylpiperazine can be easily analysed in less than 30 minutes using a photometer or colorimeter.

Sampling
Colorimeter or
l i ne
Photometer

Reagent A

Reagent B

0.225

Hold 30℃
for 20 min.

Figure 10: Field analysis procedure

Conclusion
A group of N-amino substituted heterocyclic compounds has been successfully investigated by
experimental boiler studies for their application as oxygen scavengers in boilers and other steam
generating systems. Especially 1-amino-4-methylpiperazine has been evaluated to be an effective
replacement for hydrazine in such applications. Due to its high thermal stability and high reactivity
with dissolved oxygen in the water this new oxygen scavenger is showing better performance than
other existing hydrazine replacements. Furthermore it has lower toxicity than most of the other oxygen
scavengers currently applied on the market. The new oxygen scavenger has been applied already in
about 100 industrial boiler systems and in all cases the results from the experimental boiler studies
have been confirmed. Boiler inspections after application of the new oxygen scavenger showed the
same excellent corrosion inhibition and formation of a dense magnetite layer that has been observed
with the application of hydrazine before. Analysis of the new oxygen scavenger is very simple and can
be conducted in the field within 30 minutes.
References

Cuisia, DG, Lawson, ES, Gabris, P and Fryer, M, 1993. A new generation in oxygen scavenging.
Proceedings of the International Water Conference 54: 275-282

DHEW (NIOSH), 1978. Occupational Exposure to Hydrazines. Publications No. 78 – 172, U.S. Dept.
of Health, Education and Welfare, National Institute for Occupational Safety and Health: 1-168

Jonas, O, 1990. Controlling oxygen in steam generating systems. Power 5-1990: 43

Jonas, O, 1987. Deaerators – An overview of design operation, experience and R +D. American Power
Conference, Chicago, IL

Schabacher, W, 1982. Regulatios on hydrazine as operating substance (in German). VGB

Kraftwerkstechnik 62: 139-144

Thompson, HW, 1989. Potential corrosion problems in economizers, superheaters and boilers during
operation and outages. Pulp and paper Canada, 1989 (5): T167-169

Uhlig, H, 1967. Corrosion and corrosion control. John Wiley and Sons Inc., New York: 80

Van der Wal, WJF, 1989. Experience with methyl ethyl ketoxime for oxygen removal in plant cycles
(in German). VGB Kraftwerkstechnik 69: 296-299

Zimmermann, M, 1948. A new technique for chemically degassing boiler feedwater (in German). Mitt.
VGB, No. 2/3: 70-73