Nace 2019 12816

Paper No.
12816
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SOME RECENT CORROSION PROBLEMS IN THERMAL DESALINATION PLANTS
Roger Francis
RFMaterials
Hadfield
Glossop, SK13 1QN
UK
ABSTRACT
Copper alloys are widely used for the heat exchanger tubes in both multi-stage flash (MSF) and
multiple effect distillation (MED) thermal desalination plants. Millions of metres of such tubing have
been used and, generally, the copper alloys give good performance. In the last few years the author
has looked at a number of failures from thermal desalination plants in the Middle East. These are not
from one location, but have occurred in different areas in different plants. The failure mechanisms are
also different in each area. The common feature of the failures is that the corrosion mechanism for
each one is well understood, and they could all have been prevented by using a corrosion engineer at
the design stage. This paper presents some of the diverse range of case studies and explains how
they could have been prevented.
Key words: Desalination, heat exchangers, aluminium brass, copper nickel
INTRODUCTION
In many parts of the world fresh water is in short supply and additional water is often supplied by
desalination of seawater. Two techniques commonly used for many years are MSF and MED. Both of
these are thermal processes using steam as a source of heat and have many heat exchangers to
encourage evaporation of vapour from the seawater and condensation as low chloride drinking water.
Copper alloys have a long history of successful use in these heat exchangers and for the most part
they perform very well1. The various corrosion mechanisms that can cause failure of copper alloy heat
exchanger tubing are well understood, as are methods for avoiding these problems2. Despite this the
author is regularly asked to examine failed heat exchanger tubes from thermal desalination plants. The
failure mechanisms are not unusual and the employment of a corrosion engineer at the design stage
could have avoided the vast majority. This paper discusses four case histories, all from different parts
of both types of thermal desalination plants.
PLANT OPERATION
MSF Plants
©2019 by NACE International.

Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to
NACE International, Publications Division, 15835 Park Ten Place, Houston, Texas 77084.
The material presented and the views expressed in this paper are solely those of the author(s) and are not necessarily endorsed by the Association.
1
The multi-stage flash distillation process is basically similar to distillation by boiling. Water can be
made to boil just as effectively by reducing the pressure as by raising the temperature. In a closed
vessel, the temperature and pressure are roughly proportional so that a decrease in pressure can
cause instantaneous boiling of some of the water, with the characteristic “flashing” off of some of the
water vapour.
A multi-stage flash distillation plant consists of a series of chambers (often 20 or more), each operating
at a pressure lower than the preceding one. As heated brine flows from one chamber to the next, some
of it flashes off into vapour at progressively lower temperatures. The vapour passes through demisters

to remove any entrained brine droplets and then condenses on cooler condenser tubes. The distillate
then drops into collection trays and passes from stage to stage in a distillate channel, prior to
distribution as drinking water. This usually involves the injection of CO2 (sometimes in the form of non-
condensable gases extracted from the distiller) to lower the pH. This distillate is then passed through
limestone beds to increase hardness and finally has a small quantity of chlorinated seawater added to
provide some minerals and also to disinfect the final product.
FIGURE 1 Schematic diagram of an MSF desalination plant.
The basic MSF process is shown schematically in Figure 1. Steam heats the recirculating brine in the
brine heater and the steam condensate produced is returned as feed to the boilers. The hot brine
(typically 110°C) then passes through a series of flash chambers in the heat recovery section, each at a
lower pressure than the preceding one. In each chamber, some water vapour flashes off, as described
above. In the last few heat rejection stages cold, aerated seawater is pumped through the condensers
to lower the temperature for further condensation to occur and to remove the heat in the heat input
section and complete the operating cycle.
Some of the raw seawater is discharged to waste and some is deaerated and dosed with chemicals to
control scaling and foaming, before being added to the recirculating brine as feed make-up. The feed is
necessary to replace evaporative losses and to maintain the recirculating brine concentration at
acceptable levels. The brine is then heated in the heat recovery condensers before returning to the
2
heat input section again. Because of the need for a supply of high temperature steam, MSF plants are
usually built in conjunction with a power station.
MED Plants
MED plants, like MSF plants, require a source of heat, which can be steam or hot water (MED only) or
electricity, and so are often run in conjunction with a power station. In most MED plants, a thermo-
compressor or a mechanical vapour compressor is added to improve efficiency. These are known as

thermo-compression distillation (TCD) and mechanical vapour compression (MVC) plants, respectively.
The higher efficiency of TCD plants means that they are the most common variant.
FIGURE 2 Schematic diagram of an MED desalination plant.
Figure 2 shows a typical 4-stage TCD plant, although it may contain from 2 to 14 stages. Vapour at
~75°C is introduced into the first stage evaporator tubes, where it is condensed by externally sprayed
raw water. In cooling the evaporator tubes, the raw water in stage 1 is heated and part of it vaporizes.
The vapour enters the tubes of the second stage, is condensed by raw water, as in stage 1, forming
more condensate. This process repeats itself in the subsequent stages. Part of the vapour produced
in an intermediate (fourth in Figure 2) stage is drawn up by the thermo-compressor, which increases its
pressure and mixes it with high pressure steam (Figure 2) to feed the first stage. The remainder of the
vapour passes to the following stages and finally to a heat exchanger, where it condenses on the
outside of tubes cooled internally by raw water. Part of this raw water becomes the feed to the four
stages and the rest goes to waste. The product water is collected and piped away (location 5 in Figure
2), while the brine goes to blow down (location 6).
An MED plant operates in the same way, but without the thermo-compressor. In an MVC plant the
thermo-compressor is replaced with a mechanical vapour compressor.
HEAT EXCHANGER ALLOYS
MSF Plants
Copper alloys are widely used in all the heat exchangers in an MSF plant, but the alloy used varies
somewhat. 66/30/2/2 Cu-Ni-Fe-Mn (UNS C71640) is commonly used for the tubes in the brine heater,
while 90/10 copper-nickel (UNS C70600) is very common in the heat recovery section1. The tubes in
the heat rejection section may be 90/10, 66/30/2/2, or sometimes titanium where the seawater is very
aggressive1.
MED Plants

3
Copper alloy tubes are widely used in the evaporators of MED plants and the most common are thin
wall (1.0 mm) aluminium brass (C68700) and 90/10 copper-nickel. Because of the risk of impingement
damage under the spray heads, it is usual for the top two or three rows of tubes to be titanium. The
evaporators are very different to the flash chambers in an MSF plant, in that seawater is on the outside
of the tubes in an MED plant.
CASE HISTORIES

Case History 1
A large MSF plant in the Middle East was experiencing numerous failures of 66/30/2/2 copper-nickel
tubes in the heat rejection section. The plant consisted of 12 trains, with one brine heater, 19 stages of
heat recovery and two stages of heat rejection in each train. As the tubes were ~20 m long, this was a
lot of copper alloy tubing.
Front
Middle
End
(A)
Front
Middle
End
(B)
FIGURE 3 Appearance of the 66/30/2/2 Cu-Ni-Fe-Mn tubes.
A) Corrosion only in the centre, B) Corrosion along the whole length

4
A preliminary examination identified sulphide in the corrosion products, but testing of both the feed
seawater (Red Sea) and the flue gas desulphurization plant outflow showed no sulphides were present.
Some of the tubes showed normal thin, brown films at the tube ends, but clear signs of corrosion in the
centre, while others showed corrosion over most of the tube (Figure 3).
The tubes were covered in a brown/black product with lots of mounds covering pits. Inside the pits was
a yellow/green product, which gave a strong result for sulphide using the sodium azide test (Figure 4)3.

(A)
(B)
FIGURE 4 Pits in 66/30/2/2 copper-nickel tubes.

A) General appearance, B) Close up of Figure 4A.

5
Sulphide is well known to accelerate corrosion of copper alloy heat exchanger tubes, particularly
66/30/2/2 copper-nickel2. The pitting was clearly due to sulphide, but the source was not obvious.
During discussions it emerged that there had been a number of extended shutdowns of various trains
due to other plant problems. Some of these had lasted several weeks.
The seawater feed to the heat rejection section was via fiberglass reinforced plastic (FRP) pipes over
1 m in diameter and several hundred meters long. These pipes were not drained during shutdown, and
during long periods of shutdown the dissolved oxygen would be quickly consumed by the aerobic

bacteria. Then the anaerobic bacteria, particularly sulphate reducing bacteria (SRB) would become
active, producing H2S as a metabolic by-product. At the next shutdown more than 15 mg/L sulphide
was detected in the stagnant water after 15 days.
(A)
(B)
FIGURE 5 Appearance of tubes after ferrous sulphate dosing.

A) Well filmed tube, B) Tube with slight pitting.

6
At the start up most of this sulphide polluted seawater would be flushed through the heat rejection
section in ten minutes or so. However, there were numerous dead legs and the slow leaching of
sulphide from these into the main seawater stream would mean that conditions were very aggressive
for an extended period. It is well established that as little as 0.01 mg/L sulphide in aerated seawater
will accelerate the corrosion of 66/30/2/2 copper-nickel, and more so if chlorine is also present as an
anti-foulant4.
An eddy current survey revealed that many of the tubes in some stages were very badly corroded and

these needed replacing. In order to prevent further sulphide attack it was necessary to keep stagnant
seawater out of the feed piping. Near the first stage of the heat rejection section there was a gas vent
pipe and this was re-directed to waste so that there was a slow flow of chlorinated seawater in the feed
pipe during shutdown. At the same time ferrous sulphate dosing was instituted after the re-tube to
accelerate the formation of protective films2. The dosing level was 1 mg/L Fe2+ for one hour per day,
and this was carried out for 30 days. At the end of this time some further tubes were examined.
Many of these had protective films and no sign of pitting, but a few showed signs of sulphide with the
sodium azide test (Figure 5). Clearly some tubes had been left full of water during a shutdown.
However, the attack was shallow and it was judged that better draining of the heat exchangers during
shut down would alleviate this problem.
Case History 2
When an MSF plant is shut down, the steam is not vented but is quenched in the dump condenser and
the condensed water goes to the boiler feed on start up. One dump condenser in an MSF plant was
showing severe leaks, and the tubing alloy was 66/30/2/2 Cu-Ni-Fe-Mn. Dump condensers are often
elevated and may be tens of metres above ground. This means that the syphon effect can be used to
increase water flow through the condenser and reduce demand on the pump. Figure 6 shows the
appearance of one of the tubes, with clear signs of erosion corrosion. All the attack was near the outlet
and towards the bottom of the condenser.
FIGURE 6 Appearance of 66/30/2/2 Cu-Ni-Fe-Mn tubes from dump condenser.
The attack was typical of syphonic air release, as shown schematically in Figure 7. Gas is released
under syphonic conditions, and the turbulence caused by this can result in severe erosion corrosion,
even for an alloy like 66/30/2/2, which is very resistant to erosion corrosion.

7
FIGURE 7 Schematic diagram showing syphonic air release (water flow clockwise).
An analysis of real condensers shows that the inlet and outlet sections of the second pass are most
susceptible to attack5. Syphonic air release does not occur if the pressure in the tubing is maintained
above 60 kPa (0.6 bar)5.
The solution was to adjust the valves in the seawater system to maintain an adequate pressure in the
condenser tubes. An eddy current survey showed just a few tubes near the bottom were severely
attacked and these were plugged. Since then there have been no further problems.
Case History 3
An MED plant in the Middle East was suffering numerous failures in the evaporator tubes. The top
three rows of tubes were titanium and the rest were aluminium brass. Figure 8 shows the appearance
of some typical leaking tubes. The failures were mostly in the upper tubes and down the sides of the
evaporators. The appearance of the films on the tubes in Figure 8 is typical of those that form in
natural seawater. The seawater was continuously chlorinated to control fouling and the concentration
was measured 3 times per day at the settling tank. The seawater to the spray nozzles was dosed with
the usual anti-scaling and anti-foaming chemicals.
At high magnification the attack was clearly erosion corrosion (also known as impingement attack),
sometimes as a series of smaller pits and sometimes as one large pit (Figure 9). The polymer spray
nozzles also showed clear signs of erosion corrosion (Figure 10).
The seawater intake was a 750m long closed culvert feeding water to a settling tank, which then fed all
the MED trains. The settling tank was 4m deep but was found to contain between 0.9 and 1.5m of silt.
There were reports of rubble being dumped on the coast about 700m from the main seawater intake as

8
part of an extensive land reclamation project. The silt was clearly causing the erosion corrosion and it
may have been washed down the coast from the reclamation project.

FIGURE 8 External appearance of leaking aluminium brass tubes from an MED evaporator.
FIGURE 9 Erosion corrosion (impingement) pits on outside of evaporator tube.
The following actions were suggested to prevent the erosion corrosion.
a) A hydrology survey to see if settling of silt outside the plant could be encouraged.
b) Dredging of the settling tanks to clear all pump suction intakes.
c) Fit self-cleaning filters in each of the feed lines to the spray heads.

9
The combination of these actions should remove all risk of further erosion corrosion.
NEW
USED

FIGURE 10 Erosion corrosion of polymer spray nozzles.
Case History 4
An MSF plant in the Middle East was having failures in the tubes in the heat recovery section, as shown
in Figure 11. The effects were not confined to one location in the heat recovery section. The tubes
were 90/10 copper-nickel and were suffering corrosion on the outside all along the tubes, with very
severe attack at the baffle plate locations. There was no significant attack on the inside of the tubes,
containing deaerated brine.
FIGURE 11 External appearance of 90/10 Cu-Ni tubes from heat recovery section.

10
FIGURE 12 External erosion corrosion of 90/10 Cu-Ni tube in heat recovery section.
FIGURE 13 Severe erosion corrosion of 90/10 Cu-Ni tube at a baffle plate location
The attack, both along the tubes and at the baffle plate locations, showed all the typical features of
erosion corrosion, as shown in Figures 12 and 13. On the outside of the tubes in the heat recovery
section there is mostly water vapour, with some CO2 and a little oxygen (ppb). Higher oxygen contents,
outside specification, would not cause this type of attack as oxygen encourages passivation of copper-
11
nickel alloys. However, CO2 can reduce the pH to 4.5 or less if the concentration is high6, by the
formation of carbonic acid.
The protective film on 90/10 copper-nickel is basically cuprous oxide, which is theoretically stable
above pH 4, but is easily disrupted at pH values below 5.5. The author has seen erosion corrosion of
90/10 copper-nickel in a low chloride water at pH 4.5 to 5, at velocities normally acceptable for this
alloy. It appears that cuprous oxide can form at pH values from 4 to 5.5, but it is not as stable or
protective as at near neutral pH and above. High flows of water droplets saturated with CO2 could

cause erosion corrosion of copper-nickel at low pH values. Oldfield and Todd describe the conditions
for CO2 corrosion of copper alloys under heat recovery conditions6.
The accelerated attack of the copper-nickel tubes at the baffle plates, which were made of 316L (UNS
S31603) stainless steel, could be galvanic corrosion, or it could be due to the higher velocity of the CO 2
saturated condensed water through the tight tube/plate gap, or a combination of the two. However,
CO2 is normally only present at low concentrations on the vapour side, because it is vented from the
stages as it collects in the incondensable gas section of the heat exchanger. A recent survey of the
plant had shown that there was severe cracking and other damage to the venting system, which was
made of 316L stainless steel.
Clearly the conditions in the vent were too aggressive for 316L, and it was suggested that the venting
system be repaired, either in a duplex stainless steel or a nickel-chromium molybdenum alloy,
depending on the severity of conditions in the venting system. This should prevent further corrosion in
the heat recovery section.
CONCLUSIONS
1. There are clearly still corrosion problems in the heat exchangers of thermal desalination plants.
2. All of these problems are well understood, as are the measures required to prevent them.
3. The employment of a corrosion engineer, especially at the design stage, can result in substantial
savings by preventing these failures and ensuring a long trouble free life.
ACKNOWLEDGEMENTS
The author would like to thank Carol Powell and Jim Michel of Copper Development Association for
their support in preparing this paper.
REFERENCES
1. J W Oldfield, Novel Material Selection to Improve Corrosion Resistance, Report to the Middle
East Desalination Research Centre, Project 97-AS-001, Oman, 2003.
2. R Francis, The Corrosion of Copper and Its Alloys: A Practical Guide for Engineers, NACE
International, Houston, TX, USA, 2010.
3. F Fiegl, Spot Tests in Inorganic Analysis, Elsevier publishing, Amsterdam, The Netherlands,
1958.
4. R Francis, Effect of Pollutants on Corrosion of Copper Alloys in Seawater. Part 2: Sulphide and
Chlorine, Brit. Corr. J. 20, 4 (1986) 175
5. G G Page, Influence of Syphonic Conditions on Erosion Corrosion of Brass Heat Exchanger

Tubes: A Review, New Zealand J of Science 26 (1983) 415
6. J W Oldfield and B Todd, Vapour Side Corrosion in MSF Plants, Desalination 66 (1987) 171
12

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Downloaded from http://onepetro.org/NACECORR/proceedings-pdf/CORR19/All-CORR19/NACE-2019-12816/1134806/nace-2019-12816.pdf/1 by University of Kansas user on 14 February 2024

Key words: Desalination, heat exchangers, aluminium brass, copper nickel

©2019 by NACE International.

Downloaded from http://onepetro.org/NACECORR/proceedings-pdf/CORR19/All-CORR19/NACE-2019-12816/1134806/nace-2019-12816.pdf/1 by University of Kansas user on 14 February 2024

FIGURE 1 Schematic diagram of an MSF desalination plant.

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FIGURE 2 Schematic diagram of an MED desalination plant.

HEAT EXCHANGER ALLOYS

©2019 by NACE International.

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©2019 by NACE International.

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FIGURE 4 Pits in 66/30/2/2 copper-nickel tubes.

©2019 by NACE International.

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FIGURE 5 Appearance of tubes after ferrous sulphate dosing.

©2019 by NACE International.

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FIGURE 6 Appearance of 66/30/2/2 Cu-Ni-Fe-Mn tubes from dump condenser.

©2019 by NACE International.

©2019 by NACE International.

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FIGURE 9 Erosion corrosion (impingement) pits on outside of evaporator tube.

The following actions were suggested to prevent the erosion corrosion.

©2019 by NACE International.

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©2019 by NACE International.

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5. G G Page, Influence of Syphonic Conditions on Erosion Corrosion of Brass Heat Exchanger

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