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Abstract
Copper-based alloy tubes (i.e. CuNi) are extensively used in desalination plants. This is in order to complete
the heating and evaporating process for the seawater and to obtain distillate water that can be used in the steam
generation plant and as drinking water. A number of these tubes were found to suffer from severe localized corrosion
at 6 oclock position (corrosion throughout the pipe wall thickness). Several samples from the failed tubes were
subjected to metallographic examination and electrochemical test in the simulated working environment (i.e. chloride
content, temp. non evacuated system) in order to establish the main cause of corrosion and failure of the tubes.
Keywords: Condenser tube failure; Pitting corrosion; Multi-stage flash; Desalination plant; Dissolved gases
1. Background
Coppernickel alloys have a remarkable combination of good resistance to both corrosion and
biofouling in seawater. As they are also readily
welded and fabricated, they are an obvious choice
for pipe systems, heat exchangers, boat hulls and
other structures engineered for marine use.
Coppernickels have been specified for seawater use for over 50 years; they are the materials
of first choice for seawater pipe work and con*Corresponding author.
Presented at EuroMed 2006 conference on Desalination Strategies in South Mediterranean Countries: Cooperation
between Mediterranean Countries of Europe and the Southern Rim of the Mediterranean. Sponsored by the
European Desalination Society and the University of Montpellier II, Montpellier, France, 2125 May 2006.
0011-9164/07/$ See front matter 2007 Elsevier B.V. All rights reserved
141
4 m/s for the 7030 alloy. Although these guideline values are now considered to be conservative,
they work well because they take into account effects from things like bends which cause areas of
high local flow rate. Nevertheless, extreme turbulence has to be avoided from elements like tight
radius bends, partial blockages and areas downstream of partially throttled valves.
Minimum flow rates of more than 1 m/s are
usually preferred to avoid sediment build up.
4. Localized corrosion
Coppernickels have good inherent resistance
to chloride pitting and crevice corrosion. Crevice
corrosion is seldom found. The mechanism is a
metal ion concentration cell type totally different
to that of stainless steels. Coppernickels are not
susceptible to chloride or sulphide stress corrosion
cracking or hydrogen embrittlement and unlike
brasses do not suffer cracking due to ammonia in
seawater service. But ammonia can cause higher
corrosion rates, although coppernickels are more
resistant than many other copper-based alloys.
Coppernickel tubing is resistant to chlorination
at the dosing levels used to control biofouling.
Excessive chlorination can be detrimental, as it
reduces erosion-corrosion resistance.
Dealloying is not common with coppernickel
alloys. De-nickelification of the 7030 alloy has
been encountered occasionally in refinery overhead condenser service, where hydrocarbon
streams condense at temperatures above 150C.
This appears to be due to thermo-galvanic effects
resulting from local hot spots. The solution has
been to remove the deposits which lead to the hot
spots either by more frequent cleaning or by increasing flow rates. Ammonia in seawater can
produce a type of de-alloying which looks similar
to hot spot corrosion. This happens at around
ambient temperature, but only under heat transfer
conditions. It can be controlled by adding ferrous
sulphate to the seawater.
142
Fig. 1. Large hole (a) and cluster of small corrosion pits (b).
a
Fig. 2. Localized corrosion pits.
143
Table 1
Results of XRD analysis
Elements
Concentration (wt. %)
C
O
Cu
Mg
Si
Cl
Fe
Ni
2.22
27.00
51.32
0.077
0.138
9.365
1.949
7.459
XRD analysis. A sign of chloride, Mg, high oxygen and carbon were detected in the analyzed thin
film scale, this indicates that the tubes were exposed directly to seawater vapor. The heavy scale
was observed on the stainless steel demisters and
surrounding areas.
5.5. Electrochemical tests
Electrochemical study using potentiodynamic
test technique was conducted on samples taken
from the failed CuNi tubes in the environment
containing a wide range of chloride ions, air and
some of CO2 gas. The latter was made to simulate
a
Fig. 3. Wide and shallow pits penetrated throughout the wall thickness.
144
6. Discussion
The results of examination and tests conducted
on CuNi tubes for the desalination revealed the
fact that the corrosion was localized and initiated
from the external surface.
The mechanism of failure can be given as follows: the results of visual and microscopic examination revealed the fact that the corrosion was
initiated externally on the CuNi tubes. Several
localized corrosion pits (isolated and clustered)
were observed on the examined tubes at 6 oclock
position. SEM-EDAX analysis of the corrosion
products and deposit was found to compose of
cuprous oxide, high oxygen and carbon content.
The high carbon content may be from build-up of
scale (carbonate-HCO3), as a result of CO2 gas
present within the system (dissolved within the
water droplets), particularly when the vacuum
system does not working properly.
The conducted examinations on the received
tubes excluded the suggestion that the CuNi
material composition was the main cause of Cu
Ni tubes failure. The results of chemical analysis
confirm that the tubes were made of CuNi alloy
(9010).
The mechanism of Cu-Ni tubes corrosion and
failure could be attributed to the process control
problem which can be given as per these two
scenarios.
6.1. Scenario I
i
145
gen, some chloride ions, K and Na, were all detected at areas around the localized corrosion sites
(pits).
The present thin film of scale may have created
corrosion micro-cells leading to autocatalytic
progressive in the corrosion process [1]. The corrosion process is aggravated by surrounding temperature in addition to the presence of chloride ions
within the build-up thin scale (salts, carbonates
result of CO2 and water). The presence of this film
in wet condition in addition to the dissolved gases
CO2 and O2 is expected to aggravate the corrosion
process via formation of carbonic acid and reduction of pH.
The conducted electrochemical tests confirmed
that CO2 gas alone seem to be not enough to cause
severe or localized corrosion on CuNi tubes/
material and the chloride ions in concentration
more than 100 ppm need to be present, as shown
in Fig. 4. The corrosion was found to be pronounced when the chloride ions concentration was
found to be more than 1000 ppm in presence of
CO2 as shown in Fig. 5. Highest corrosion rate
was expected when high concentration of chloride
ions (22,000 ppm Cl ions H seawater) was present
along with CO2 gas as shown in Figs. 46. The
requirements to chloride ions may be due to the
fact that pH was not low enough to cause corrosion.
6.2. Scenario II
The other suggested mechanism can be given
as follows:
The effect of vapor side environment is expected to play some role in Cu-Ni tube corrosion.
The surrounded environment is steam contains
CO2 and oxygen gases [1]. The non condensable
CO2 gas is expected to form low pH carbonic acid,
in the vapor zone leading to increased vapor side
corrosion (VSC).
As mentioned above, most desalination units
have inadequate venting system (small, not efficient etc.) and some gas like CO2 and oxygen is
expected within the system. The condensed vapor
146
8. Recommendations
1. Identify the source of seawater salts found
on CuNi tubes as a result of internal corrosion
leakage or as a result of demister/vacuum problem.
The presence of chloride ions was confirmed by
EDAX analysis.
2. Check the performance of the vacuum system of the desalination unit(s). This is an important
step and need to be considered. Presence of gases
shall assist in initiation and acceleration in the corrosion process.
References
[1] G.J. Danek and R.B. Niederberger, Accelerated
corrosion of coppernickel alloys in polluted waters,
Corrosion/76, Paper No.76, NACE, 1976.
[2] A. Syrett, Accelerated corrosion of copper in flowing
pure water contaminated with oxygen and sulfide,
Corrosion, 33 (1977) 257262.
[3] C. Giulani and G. Bombard, Influence of pollution
on the corrosion of copper alloys in flowing salt
water, Br. Corrosion J., 8 (1973) 2024.
[4] R. Dooly and J. Glater, Alkaline scale formation in
boiling sea water brines, Desalination, 11 (1972) 1
16.
[5] M.A. Finan and M.N. Elliot, A theory of the formation of magnesium scales in sea water distillation
plants, and means for their prevention, Desalination,
14 (1974) 325340.