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A Corrosion Inhibitor For Stave Cooler

Of Blast Furnace
T-h Choi and S-h Shim*
Pohang Iron & Steel Co Ltd, *Acculab Co Ltd

SUMMARY:.A new corrosion inhibitor was developed for prolonging service life of a closed-loop
cooling system. It consists of nitrite, organic polymer, etc. The chemical forms the corrosion
protection layer on the surface of cooling pipe. It also increases the solubility of scale materials into
the cooling water and prevents building-up of scale compounds. It is very effective in the closed
cooling system. To compare the relative performance of the conventional inhibitors with the new
one in high hardness water, process simulation tests were carried out. In this high hardness water
the anti-corrosion performances of the conventional inhibitors turned out to be poor. However, the
program with the new inhibitor showed a very low corrosion rate. The corrosion rate caused by the
new inhibitor was less than 1.7MDD in the field test.

Keywords: Closed-loop cooling system, Cooling water quality, Scale, Corrosion inhibitor
1

INTRODUCTION

It is known that about 70% of industrial water is used as cooling water. The industrial cooling water systems are classified into
once-through systems and recirculating systems depending upon the method of water usage. A once-through system takes its
make-up water from a sea, lake or river into the system and the heated water by the heat exchangers returns to its origin. The
water in a circulating system absorbs heat from heat exchangers or other heat releasing devices and releases heat at a cooling
tower or at other heat exchangers by evaporation. The water in a circulating system is used to absorb heat repeatedly [1-3].
A circulating system with a cooling tower is called as an open circulating system. Since this type of systems lose water
consistently by evaporation, continuous water make-up is necessary. And to avoid the mineral scale precipitation problems on
the heat exchanger surfaces by mineral concentration in water by evaporation, continuous or intermittent blow-down is
essential. A circulating system without cooling towers is called a closed-loop cooling system. Since the water in a closed-loop
cooling system stays in the system for a long time a proper chemical water treatment with relatively high concentration can
prevent metal corrosion and mineral scale problem successfully.
When a closed-loop cooling system is large and has complicated structure, the replacement of the failed parts is usually very
expensive and difficult. Therefore, it is essential to maintain good chemical water treatment to minimize metal corrosion and
mineral scale formation in the system. The unexpected failure of a system by corrosion can cause dangerous explosion when
cooling water leaks into a high temperature reactor. The formation of scale on the heated surface also can cause a distortion of
the system and lead to a failure.
Chromate was used in the closed system for corrosion prevention of mild steel in the past. Since chromate is carcinogenic and
low dosage treatment causes pitting corrosion it is not widely used these days. In some cases caustic is used to raise water pH,
to lower the dissolution rate of iron and to form passive film on the metal surface. When the closed system is airtight sodium
sulphite or hydrazine is used to remove oxygen in the cooling water for minimizing corrosion. When sodium sulfite and
caustic are used to control metal corrosion, the salts such as sodium sulfate, calcium carbonate, calcium hydroxide, calcium
phosphate, calcium sulfate and silicone hydroxide tend to form scales on the metal surface leading to cause trouble [4,5].

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2
2.1

EXPERIMENT
Apparatus

An experimental refluxing apparatus was used to select the chemicals for corrosion and scale inhibition properties in short time
as shown in Figure I. The apparatus was composed of a hot plate, an Erlenmeyer flask, a magnetic stirrer and a steam-cooling
device. The steam-cooling device was employed to maintain the water level. The temperature of water could be controlled in
the range of 20 to 100oC.

Cooling
water(in)

Composite
cooling
water

Cooling water
(out)

Coupon

Spin bar
Hot plate

Figure I. Experimental apparatus.

A pilot system was designed and constructed to simulate the real closed recirculating cooling systems. This system has a
double layer tube section. Cooling water flows through the inside tube and water heated by electrical heater flows through the
annular space between the two tubes. The inlet and outlet temperatures of heating and cooling water were monitored during
the tests.
A test column with a mild steel coupon was placed in a real system to test the performance of the developed chemical program
for corrosion and scale control. The coupons were examined after one-month test period and water was analysed every week.

2.2

Experimental method

The water analysis was performed using a UV-visible spectrophotometer, a pH meter and a conductivity meter.
Calcium carbonate and sodium bicarbonate were added by 200 ppm of Ca++ and HCO3- concentrations respectively in distilled
water to speed up the scale formation. The corrosion rate and the scale formation rates were calculated by the following
equations.
Corrosion Rate (MDD) = (original coupon weight (mg) - coupon weight after cleaning (mg))
! 100 / (coupon surface area (cm2) ! test days (day))--------------------------------- (1)
Scale Rate (MCM) = (coupon weight after test (mg) - coupon weight after cleaning (mg))
/ (Coupon surface area (cm2) ! test months (M))--------------------------------------- (2)

2.3

New chemical program

The conventional treatment programs contain inorganic phosphates and oxygen scavengers such as sulfite or hydrazine. It is
essential to replace cooling water periodically to prevent the phosphate salts forming scale on the mild steel tube surfaces. It is
very difficult to drain the water fully for complicated system such as the stave cooler of a blast furnace. Therefore a chemical
treatment program was developed not only to prevent metal corrosion but also to prevent mineral scale formation without
replacing cooling water by increasing the solubility of the scale forming mineral salts. The chemicals, which increase the
solubility of the scale forming mineral salts, are listed in Table I.

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The typical anodic corrosion inhibitors used for closed cooling systems were tested by the refluxing system shown in Figure I.
The change in corrosion rate of STPG400 mild steel coupon at 40oC with changing the inhibitor concentration is shown in
Figure II. STPG400 mild steel was chosen because it was the material for the staves of the blast furnaces. From the figure,
molybdate and nitrite showed better corrosion inhibition than chromate. These two chemicals showed the best performance
when the concentration reached above 1000 PPM Since molybdate was expensive, nitrite was chosen for this study. Nitrite is
an oxidizing anodic corrosion inhibitor for mild steel. It forms very thin and protective -Fe2O3 on a mild steel surface.
However, it is converted to nitrate by nitrifying bacteria and lose corrosion inhibition property [1]. It was inferred that it was
appropriate to use nitrite in a relatively high temperature closed cooling system because it was unlikely to have nitrifying
bacteria problem [1].
A number of organic phosphates and polymer dispersants were examined to inhibit the formation of mineral scale. The organic
phosphates were known to be effective to prevent calcium carbonate scale formation, however, thermal decomposition could
occur when cooling water temperature reached close to

Che mic a ls
Co rr os io n
inhibitor

Chr oma te
Moly bda te
Nitr ite

S c a le
inhibitor

P OE;poly ole s te r
T EA P ;tr ie tha nola mine pho s pha te
A MP;a minotr is me thy le ne pos pho nic a c id
HEDP ;1- hy dr ox y e thy lide ne - 1 ,1 - dipho s phonic a c id
P B T C;2 - phos pho no buta ne - 1,2 ,4 - tr ic a r box y lic a c id
HP A ;hy dro x y - phos phonoa c e tic a c id
EDT MP ;e thy le ne dia mine te tra me thy le ne phos phonic
a c id

Table I. Chemicals for corrosion and scale inhibition

10

C hrom ate

M olybdate

Sodium nitrite

Corrosion rate(MD

0
0

200

400

600

800

1000

1200

1400

1600

C oncentration of inhibitor(PPM )

Figure II. C orrosion rate w ith various anodic inhibitors.

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100oC. The stabilities of the organic phosphonates can be tested by measuring ortho-phosphate ion concentration in cooling
water with time [2]. Table II shows the time for each phosphonate to indicate measurable ortho-phosphate concentration by
decomposition.

Phos pa t e s

Te mpe r a t ur e of wa t e r ( )
40

AMP

80
38

100

HEDP

1056

2. 5

PBTC

1080

28. 0

4. 0

Table II. Time for appearance of PO4 ions (hr.)

PBTC was chosen for the calcium carbonate scale inhibitor for this project because it showed the best thermal stability among
the tested phosphonates. PBTC modifies the structure of calcium carbonate particles by chemisorbing on the surface
[10,13,14]. This type of scale inhibition mechanism is called as threshold inhibition. PBTC also forms thin iron oxide film to
protect mild steel corrosion by colloidal type reaction with iron hydroxide [3].
A series of experiments were performed to test the corrosion inhibition properties of the organic propionates by using the
instrument shown in Figure I. In Figure III the test results show clearly that the addition of the phosphonates inhibits corrosion
of mild steel. However, overdosing of the chemicals increased the corrosion rate. The optimum dosage of the chemicals was
about 20 P.P.M.
Polymers or co-polymers are used to prevent corrosion or scale products to adhere on the metal surface. The molecular
weights of these materials are several thousand to several hundred thousand. They inhibit the growth of the scale particles and
modify the properties of the particle surface without adhering on the metal surface. Small amount of copper corrosion
100

AMP

HEDP

PBTC

80

Co
rr
os
io
n
ra
te
(M
DD
)

60

40

20

0
0

20

40

60

80
100
Concentration
inhibitor(PPM)

120

140

160

180

200

of

Figure III. Corrosion rate with various cathodic inhibitors.

inhibitor was added in the chemical program to protect the copper alloy parts of a cooling water pump and valves. The copper
corrosion inhibitors used for this research were mercaptobenzo-thiazole, benzotriazole or tolyltriazole. These materials
chemisorb on the copper alloys and prevent electrochemical corrosion of the metals.
The developed chemical program contains 23-27% nitrite, 0.3-0.7% organic phosphate, 0.4-0.7% dispersant polymers and 0.10.3% copper corrosion inhibitor. This program was added to the cooling water to control the nitrite concentration at 600-1200
ppm.

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3
3.1

RESULTS AND DISCUSSION

The effect of chemical treatment

The concentration effect of the newly developed program on mild steel (STPG400) corrosion was measured using the
apparatus shown in Figure I. Figure IV shows the corrosion rate and the scale adherence rate. The corrosion rate of the mild
steel coupon reached almost zero when the chemical program concentration was about 100 ppmThe scale formation rate also
reached almost zero when the concentration was about 100 ppm.
One-month tests were carried out using the same cooling water chemistry to compare the conventional treatment programs
with the newly developed one. The conventional programs contain inorganic phosphate, hydrazine and dispersant polymers.
The test results are shown in Table III. From the table, several conventional programs showed very high corrosion and scale
rates to be used for a closed circulating cooling water system and the other conventional ones also showed much higher
corrosion and scale rates than the one (chemical brand: POSLAB) developed for this study. The mild steel coupon in the water
100

50
Corrosion

Scale Adherence

80

40 Sca
le
adh
ere
nce
30 rat
e(M
CM)

Cor
ros
ion
rat 60
e(M
DD)
40

20

20

10

0
1

10

100

0
10000

1000

Concentration
inhibitor(PPM)

of

Figure IV. Effect of inhibitor concentration on corrosion and scale adherence rate.
with the newly developed chemical program showed no sign of corrosion and the surface was very clean. The water in the
flask after each test was examined. The water with the conventional treatment programs showed milky or brown color,
however, the one with the new program showed no sign of mineral precipitation. Table IV shows the chemical analysis of the
water after tests. Two conventional programs showed zero total hardness because all the hardness was precipitated as
particles. The precipitation made the water milky and these scale products might adhere on the metal surface if water was not
drained from the system in time.

No

Corros ion
r a te (MDD)

S c a le a dhe r e nc e Color of c ooling

r a te (MCM)
w a te r

Che mic a l bra nd

1 .2 1

1 3.5

lig ht milky

C0

0 .65

6 .2

milky

K2

0 .86

8 .5

milky

K6

142

4 5 .1

re d brow n

K1

8 3.6 2

2 3 7 7 6 .6

y e llow br ow n

U0

1 .7 8

5 .3

lig ht brow n

C0

0 .0

0 .0

c olor le s s

P OS LA B

5 9.0

1 9.1

lig ht brow n

w ithout inhibitor

Table III. Corrosion rate and scale adherence rate

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No p H( - )

T .Ha r d Cl
P O4
T .F e
Co nd
T urb
Che m ic a l b r a nd
( p pm )
( p pm ) ( p pm ) ( p pm ) ( S /Cm ) ( F A U)

7 .6

472

362

0 .6 9

0 .1 4

1499

2 .5 4

Or ig na l c o o ling
w a te r

7 .3 1

43

412

3 4 .2

0 .2 5

1253

3 1 .0

C0

9 .8

439

508

0 .2 8

4690

5 2 .0

K2

1 0 .4

433

3 1 .6

0 .2 4

4660

2 0 .0

K6

7 .7 2

4 6 .5

402

4 0 2 .6 4 8 .8

1247

267

K1

8 .2

448

355

3 0 .8

1 2 .3

1510

114

U0

8 .7

383

496

137

0 .5 9

1878

217

C0

7 .6

464

369

3 8 .9

0 .1 8

12580

3 .3 8

P OS L A B

7 .8

380

372

0 .6 6

1 .1 4

1092

3 2 .8

w itho ut
inhib ito r

Table IV. Chemical analysis of cooling water

3.2

2 Field application

The newly developed treatment program was applied to the stave system for a blast furnace. The mild steel coupons installed
inside the test column, which was placed between two staves, were examined after one-month test. The corrosion rate of the
mild steel coupon was 19-33 MDD when the conventional program (K1 inhibitor) was used. Figure V shows the corrosion
rate decreased to less than 1.7 MDD when the treatment program was switched to the new one. The scale formation rate was
increased slightly to about 0.04 MCM shown in Figure VI, however, it did not seem to be a problem because the standard scale
rate was 5 MCM.
50

40
With

With
inhibitor

POSLAB

C
o
r 30
r
o
s
i
o
n 20
r

10

0
98.Aug

99.Ja

Mar

May
Time(month)

Figure V. Corrosion rate of closed-loop cooling system.

Corrosion & Prevention 2000 Paper 108 Page 6

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Sep

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The water analysis showed that the pH of cooling water increased by about 1-1.5 with new program. The conductivity and
0 .1

Ad

0 .0 8

he

W ith K in h ib ito r

re

W ith P O S L A B in h ib ito r

nc
e

0 .0 6

ra t
e
of
sc

0 .0 4

a le
(M
0 .0 2

0
'9 8 . A u g

O ct

Feb

A p ril

J une

A ug

T im e (m o n th )

Figure VI. Scale adherence rate of closed-loop cooling system.

total hardness of water increased when the new program was applied. This effect seemed to be related with the solubility
effect of hardness salts by the new program. Total iron concentration and turbidity of cooling water did not change
significantly with changing the programs.

CONCLUSIONS

1.

A new closed cooling water corrosion and scale inhibitor program was developed.

2.

The new program showed clean-up effect of the pre-formed iron oxide scale.

3.

The application of the new program in a blast furnace stave system showed less than 0.17 MDD corrosion rate and 0.04
MCM scale rate.

4.

The new program turned out to be easier to use because periodic water drain was not necessary compared with the
conventional program.

5.

Periodic acid cleaning seemed unnecessary if the new program was applied.

REFERENCES

1.

Betz Laboratories: "Betzdearborn Handbook of Industrial Water Conditioning", 9th ed., Betz
Laboratories, Inc., Trevose, PA, pp231-240 (1991).

2.

M. Starostina, A. Smorodin & L. Gal-Or: Material Performance, March, pp52-65 (1999).

3.

G. Bohnsack: VBG KRAFTWERKSTECHNIK, 66, pp47-54 (1986).

4.

J. Weber: Br. Corros. J., 14, pp69-75 (1979).

5.

B. R. Grotefend: Iron and Steel Engineer, June, pp46-54 (1980).

6.

A. E. Stafford: Corrosion Prevention and Control, Oct, pp11-17 (1979).

7.

J. W. Lee: CEP, July, pp56-63 (1980).

8.

A. Marshall, B. Greaves and M. Everett: Materials Performance, May, pp45-48 (1986).

9.

R. Walker: Corrosion, 32, pp33-35 (1976).

10.

I. Drela, P. falewicz and S. Kuczkowska: Water Res., 32, pp3188-3190 (1998).

11.

P. J. Sullivan: CTI Journal, 16, pp62-67 (1994).

12.

D. J. Banerjee: Corrosion & Maintenance, July, pp193-196 (1981).

13.

T. B. Fielden and G. Stockton: Br. Corrosion Journal, 2, pp87-90 (1967).

14.

P. Dairat and C. Suneath: Langmuir, 13, pp1791-1795 (1997).

15.

G. K. Gonma: Materials Chemistry and Physics, 56, pp27-30 (1998).

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