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Evaluation of Water Corrosivity Using a Corrosion Rate Model for a Cooling Water System
Alberto Alvarez Gallegos1 , Susana Silva Martinez1 , Jos Luis Ramirez Reyes2
1 Instituto
2 CITCOR.
( Received September 24, 2004 ; received in revised form December 28, 2004 )
Abstract: The first part of a corrosion inhibitor model has been developed to be used in a specific Mexican Power Plant. The model takes into
account the main operational conditions found in the cooling water, such as major corrosive chemical species, a wide pH range, the performance of
a commercial corrosion inhibitor (based on tolyltriazol) and the material of the condenser (admiralty). The objective is to replace the old criteria
based on Langelier Saturation and Ryznard Stability Index for a better approach that can suggest a variable inhibitor dosage to achieve a desired
mpy value in the cooling water system (e. g. 1 mpy). Five pairs of admiralty coupons were sunk in five different beakers containing synthetic cooling
water with an increasing concentration factor (1 to 5) at fixed pH and temperature. The experiment was repeated at different corrosion inhibitor
concentrations, testing three different pH values (6, 7 and 8). Admiralty corrosion rates were obtained (from 0.04 to 2.7 mpy) in the laboratory,
in the presence and absence of a commercial corrosion inhibitor, using a jar test and synthetic cooling water. The corrosion rates in admiralty
were assessed by means of the Linear Polarization Resistance technique. It is demonstrated that, basically admiralty corrosion rate is a function of
water chemistry, pH and corrosion inhibitor concentration. Experimental data can be fitted to an empirical equation to predict the performance of
a corrosion inhibitor versus inhibitor dosage. The model runs in a personal computer allows the prediction of information related to the treatment
cost to achieve a desired mpy value in the cooling water system.
Key words : corrosion, indices, inhibitors, modeling.
1.
INTRODUCTION
For most recirculated cooling water systems in the electric utility industry, corrosion control is a common problem and it is
linked to condenser performance. Clean heat transfer surfaces
are essential to minimize forced outages. Optimizing the performance of cooling water system depends strongly upon the
method followed to predict corrosion in aqueous solutions.
In 1936, the Langelier Saturation Index, LSI, [1] was introduced
as the first attempt to quantify the solid-liquid equilibrium status of calcium carbonate in water. A few years latter, a new
index appeared [2], the Ryznard Saturation Index (RSI), claiming a better alternative to assess the same chemical equilibrium.
Shortly thereafter, both indices became universal tools for pre To
whom correspondence
algga56@hotmail.com
should
be
addressed:
email:
133
134
COPPER CORROSION
Copper alloys are the most common material for heat exchangers in cooling water systems using cooling towers. It is well
known that copper alloys form natural oxide film (Cu2 O) as
soon as they are in contact with water. The stability of this
film is a critical parameter because it protects the base metal
from further oxidation. In fact, this natural oxide film can be
degraded by the water chemistry impact on its surface, e. g.
chlorides, sulfates, pH, total dissolved solids, oxygen, etc.
It is accepted that the protective oxide film contains less copper
[9] than is indicated by the chemical formula. That means that
there are vacancies in the cuprous oxide lattice. In theory, copper is oxidized according to the following mechanism. At the
beginning Cu0 oxidizes to Cu+ . Then, this ion moves to fill the
gaps into the lattice. As the cuprous ion migrates through these
vacancies, the oxygen, on the surface of the metal, ultimately
oxidizes it to the cupric ion (Cu++ ). Oxygen accepts electrons
from the cuprous ion found in the cuprous oxide lattice and the
ion Cu++ is released in the bulk solution. The gap in the oxide lattice left behind could be replaced with another cuprous
ion, maintaining the oxidation process. This process could be
represented by means of the figure 1.
In order to minimize the oxidation mechanism it is necessary
to minimize the outward movement of the cuprous ion from
the metal. Selecting a good metal, neutralizing the nature and
amount of dissolved chemicals that enhance the corrosion rates
or a combination of both can solve the problem. In pure copper,
the natural oxide film, formed during corrosion, is highly defective and contains many gaps into which the cuprous ion can
(1)
Inhibitors films reinforce the resistance offered by Cu2 O in retarding the reduction of the oxygen.
3.
3.1
The first model to predict the water corrosive potential was the
Langelier Saturation Index (LSI). It can be represented by the
following equation:
(2)
Evaluation of Water Corrosivity Using a Corrosion Rate Model . / J. New Mat. Electrochem. Systems 8, 133-142 (2005)
O2 O2 (ads)
O2 (ads) + H + e HO2 (ads)
HO2 (ads) + H + + e H2 O2 (ads)
H2 O2 (ads) + 2e 2OH
135
(4)
2 4
2
2+ 3
5
CR = K (Cl )1 (SO2
4 ) (Ca ) (CO3 ) (inhib) . . . (5)
136
Where 1 , 2 , . . . n are regression coefficients; K is temperature dependent constant; inhib is a corrosion inhibitor concentration and the rest of the variables are chemical species concentrations. Because the objective of the method is to look for
the best mathematical correlation between corrosion rate and
the water chemistry, there is not a fixed limit in the number of
variables.
A11
A21
A31
A41
A12
A22
A32
A42
A13
A23
A33
A43
A14
A24
A34
A44
b1
1
2 b2
3 b3
4 = b4
(9)
A11 =
ln(Cl )k ln(Cl )k ;
A12 =
k1
Equation (6) can be solved by a multiple linear regression analysis [22]. Indeed, it is possible to find a smoothing function
g(Water Chemistry) (with parameters 1 , 2 , . . . n to be determined) whose graph is capable of assuming the shape determined by M experimental data points. In this way, the square
error E(g) is an indicator of how well g(Water Chemistry) fits
these experimental data points. This can be done by minimizing E(g), defined by:
ln(Cl )k ln(Ca2+ )k ;
A14 =
k1
k1
Where M
k1 denotes the sum over all M data points.
(7)
ln(Cl )k ln(CO2
3 )k ;
E(g) =
k1
A13 =
ln(Cl )k ln(SO2
4 )k ;
A22 =
k1
2
ln(SO2
4 )k ln(SO4 )k ; A23 =
k1
2+
ln(SO2
4 )k ln(Ca )k ;
k1
A24 =
k1
A33 =
E(g)
= 2 [g((Water Chemistry)k ln(CR)k ] ln(Cl )k
1
k1
k1
k1
M
E(g)
= 2 [g((Water Chemistry)k ln(CR)k ] ln(SO2
4 )k
2
k1
M
E(g)
= 2 [g((Water Chemistry)k ln(CR)k ] ln(Ca2+ )k
3
k1
M
E(g)
= 2 [g((Water Chemistry)k ln(CR)k ] ln(CO2
3 )k
4
k1
(8)
The set of equations in (8) are called normal equations and are
guaranteed to be linear, hence easily solved, regardless of the
2
ln(SO2
4 )k ln(CO3 )k ;
A44 =
2
ln(CO2
3 )k ln(CO3 )k ;
k1
Evaluation of Water Corrosivity Using a Corrosion Rate Model . / J. New Mat. Electrochem. Systems 8, 133-142 (2005)
6.
EXPERIMENTAL METHOD
current density plot can be considered linear in the studied region and can be represented by the following equation [23]:
icorr =
Reactor 1
CF 1
Reactor 2
CF 2
Cl
SO2
4
Ca+2
CO2
3
HCO
3
Na+
K+
Mg+2
283
480
40
0.005
73
368
39
24
567
1056
80
0.009
98
736
117
48
Reactor 3
Reactor 4
CF 3
CF 4
ppm (as ion)
851
1134
1536
2016
120
160
0.028
0.040
214
299
1104
1472
156
195
72
96
B=
Reactor 5
CF 5
1418
2592
200
0.052
354
1840
273
120
B
R
(10)
137
ba bc
2.303(ba + bc )
(11)
A pair of admiralty coupons were sunk in each beaker and Admiralty corrosion rates were assessed at room temperature, by
means of the Linear Polarization Resistance (LPR) technique
(ASTM, 1989), at three different pH values (6, 7 and 8). During the experiment, the pH was maintained constant ( 0.1 pH
units), by adding NaOH or H2 SO4 . Each set of experiments
lasted at least 4 hours. Experiments were repeated in the presence of three different inhibitor concentrations (6, 12 and 25
ppm). A schematic diagram of a representative jar test is shown
in figure 2.
7.1
138
Table 2: Experimental corrosion rates on Admiralty coupons as a function of the chemistry of cooling water, pH = 6 0.1, room
temperature and inhibitor-free. Water corrosivity prediction using LSI model [4]
Experimental Corrosion
Rate (mpy)
Assessed by LPR
LSI (Betz,1980)
Reactor 1
CF 1
Reactor 2
CF 2
Reactor 3
CF 3
Reactor 4
CF 4
Reactor 5
CF 5
1.27
1.39
1.51
2.34
2.69
-2.1
-1.7
-1.2
-1
-1
ple of water was predicted by means of LSI [4]. The main results are showed in table 2.
As expected, corrosion rate on Admiralty increases as sulfates
and chlorides concentration increase in the cooling water. Although a negative LSI was obtained (water considered corrosive) in all the reactors, the LSI magnitude indicates a wrong
prediction. According to LSI the impact of water chemistry on
Admiralty is higher in reactor 1 than in reactor 5, but the experience [7,24] and the common sense indicate the contrary.
In the absence of inhibitor a set of five experiments were performed using the chemical composition shown in table 1, at
room temperature and at two different pH values (7 and 8).
Experimental corrosion rates (expressed as mpy) on Admiralty
coupons were obtained as a function of water chemistry and pH.
The main results are shown in a 3-D graph (fig. 4)
Figure 4: Water chemistry and pH impact on Admiralty corrosion rates in absence of inhibitor at room temperature
From the figure 4, it can be seen that keeping water chemistry
constant, experimental corrosion rates on Admiralty are higher
at low pH values and they diminish smoothly toward alkaline
pH values. On the other hand, keeping a pH constant, experi-
Following the same experimental procedure than before, experimental corrosion rates on Admiralty, in the presence of a
commercial inhibitor (based on tolyltriazole) were obtained as
a function of water chemistry (see table 1) at three different pH
values (6, 7 and 8). Figure 5 shows, the efficiency of 6 ppm of
inhibitor on the Admiralty corrosion rates at room temperature.
Figure 5: Water chemistry and pH impact on Admiralty corrosion rates in presence of 6 ppm of inhibitor at room temperature
139
Evaluation of Water Corrosivity Using a Corrosion Rate Model . / J. New Mat. Electrochem. Systems 8, 133-142 (2005)
pH 6 to pH 8 and from CF 1 to CF 5. The efficiency of the inhibitor can be assessed by means of the following equation [25]:
E=
(CR0 CR1 )
100
CR0
(12)
Where CR0 and CR1 are experimental corrosion rates in the absence and in the presence of an inhibitor, respectively. Table 3
shows the efficiencies obtained for 6 ppm Inhibitor in five different synthetic cooling waters at room temperature and at three
different pH values.
1.27
0.18
86
CR0 (mpy)
CR1 (mpy)
E (%)
0.43
0.07
84
CR0 (mpy)
CR1 (mpy)
E (%)
0.15
0.05
67
2
pH 6
1.39
0.21
85
pH 7
0.61
0.08
87
pH 8
0.25
0.06
76
Reactor
3
1.51
0.36
76
2.34
0.47
80
2.69
0.56
80
0.82
0.08
90
1.04
0.12
88
1.47
0.26
82
0.30
0.07
77
0.44
0.09
80
0.66
0.17
74
1.27
0.07
94
CR0 (mpy)
CR1 (mpy)
E (%)
0.43
0.04
91
CR0 (mpy)
CR1 (mpy)
E (%)
0.15
0.02
87
2
pH 6
1.39
0.09
94
pH 7
0.61
0.04
93
pH 8
0.25
0.03
88
Reactor
3
1.51
0.10
93
2.34
0.13
94
2.69
0.16
94
0.82
0.04
95
1.04
0.05
95
1.47
0.07
95
0.30
0.04
87
0.44
0.04
91
0.66
0.04
94
1.27
0.07
94
CR0 (mpy)
CR1 (mpy)
E (%)
0.43
0.04
91
CR0 (mpy)
CR1 (mpy)
E (%)
0.15
0.02
87
2
pH 6
1.39
0.09
94
pH 7
0.61
0.04
93
pH 8
0.25
0.03
88
Reactor
3
1.51
0.10
93
2.34
0.13
94
2.69
0.16
94
0.82
0.04
95
1.04
0.05
95
1.47
0.07
95
0.30
0.04
87
0.44
0.04
91
0.66
0.04
94
140
7.3
2+
ln(CR) = 1 ln(Cl ) + 2 ln(SO2
4 ) + 3 ln(Ca )
(13)
Figure 6: Water chemistry and pH impact on Admiralty corrosion rates in presence of 12 ppm of inhibitor at room temperature
pH Region
6 pH 6.5;
6.5 < pH 7;
7 < pH 7.5;
7.5 < pH 8;
pH > 8
Figure 7: Water chemistry and pH impact on Admiralty corrosion rates in presence of 24 ppm of inhibitor at room temperature
Equation (13)
ln(CR) = 1 ln(Cl ) + 2 ln(SO2
4 )
+3 ln(Ca2+ )
1
2
3
-0.288 -0.439
1.216
-0.311 -0.415
1.088
-0.689 -0.633
1.891
-0.707 -1.270
2.820
-0.998 -1.289
3.172
Evaluation of Water Corrosivity Using a Corrosion Rate Model . / J. New Mat. Electrochem. Systems 8, 133-142 (2005)
corrosion rates at room temperature, pH 6 and different chemical composition (expressed as concentration factor, CF).
141
Modeling over the operating range encountered for pH and water chemistry, allows for optimization of inhibitor feed. A typical dosage profile, for a concentration factor of 3, room temperature and different pH values, is shown in Figure 9.
.9
142
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