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Contents
1      Introduction .......................................................................................................................................... 3

2      Corrosion in desalination plants ........................................................................................................... 3

3      Vapor-Space Corrosion ......................................................................................................................... 3

4      Corrosion in Flash Champers ................................................................................................................ 4

    4.1        The interesting features of the corrosion of flash chamber (mild steel) are as follows: .............. 4

    4.2        The major causes of the corrosion damage are: .......................................................................... 5

1 Abstract ...................................................................................................................................................... 5

5      Historical review ................................................................................................................................... 6

6      Operational experience analysis ........................................................................................................... 7

7      Development of the technology and future prospects ...................................................................... 11

8      Corrosion in desalination plant ........................................................................................................... 14

    8.1        Type of corrosion ........................................................................................................................ 14

       8.1.1           Cavitations and Impingement ............................................................................................. 14

       8.1.2           Crevice Corrosion ................................................................................................................ 15

       8.1.3           Erosion Corrosion ................................................................................................................ 16

    8.2 ........................................................................................................................................................... 16

       8.2.1           Environmental Cracking ...................................................................................................... 17

9      Copper alloy ........................................................................................................................................ 18

    9.1        Introduction ................................................................................................................................ 18

       9.1.1           Specifications, Properties and Availability .......................................................................... 18

       9.1.2           Resistance to Corrosion and Bio-Fouling ............................................................................ 21

       9.1.3           Sea Water Intakes ............................................................................................................... 24

10         Materials for Heat Exchanger Tubes ............................................................................................... 25

    10.1       Introduction ................................................................................................................................ 25
10.2      Design Requirements .................................................................................................................. 26

 10.3      The Model ................................................................................................................................... 26

 10.4      The Selection ............................................................................................................................... 28

 10.5      Results ......................................................................................................................................... 30

 10.6      PostScript .................................................................................................................................... 31

11      Materials in Seawater Reverse Osmosis (SWRO) Plants ................................................................. 32

 11.1      Use of Superior Materials ........................................................................................................... 34

     11.1.1        Flash Chambers ................................................................................................................... 34

     11.1.2        Heat Exchangers.................................................................................................................. 34

     11.1.3        Relevance of Corrosion Research in the Material Selection ............................................... 34

     11.1.4        Venting System ................................................................................................................... 35

     11.1.5        Pumps.................................................................................................................................. 36

     11.1.6        Pipings ................................................................................................................................. 37

12      Conclusion ....................................................................................................................................... 37
1 Introduction


        To build desalination plant needs a huge study of material metals, composites and non-
metals which not just meet the requirements of the design and operation but also to adapt the
nature of the environment that surround the plants. One important subject to think about
during selecting the proper material for constructing for specific unit or component is corrosion
characteristics. Desalination power plant usually exposed to different and varied types of
environment such as seawater, seawater-air and salt-air aerosols, corrosive gases, very fast or
extremely slow moving liquids, particulates contained in high velocity fluids or deposit-forming
liquids all of them create a number of corrosion related problems.


2 Corrosion in desalination plants


        Seawater desalination plant involve a lot of corrosion because of the operation in
environment that doesn’t forgive that consist of seawater, seawater-air and

salt-air aerosols, corrosive gases, very fast or slow moving liquids, particulates contained

in high velocity fluids or deposit forming liquids.


3 Vapor-Space Corrosion


          In MSF plants vapor space conditions are less well controlled and severe corrosion has

been observed in both acid and additive dosed plants at rates well in excess of the

designed corrosion allowance. Apart from water vapor which is always present,

incondensable gases evolved from the flashing brine will be present. These gases are

mainly CO2, O2, and N2. In some cases H2S and NH3 also would be present if seawater
feed to the plant is polluted with decomposing organic materials.


4 Corrosion in Flash Champers




Figure 1, Corrosion of a flash chamber (3rd stage).

        One of the most familiar construction materials for flash chapmers is the carbon steel. It is
used as such or cladded with stainless steel or Cu-Ni in early or all the stages. Epoxy coating has
also been used. Flash chambers are subjected to severe corrosion and potential metal failures.
The role of oxygen in the corrosion of metals of construction in MSF plants in general and
evaporators in particular is quite complex.

4.1 The interesting features of the corrosion of flash chamber (mild steel) are
       as follows:



Corrosion is maximum in the middle of the stages where the combined effects of
two competing factors e.g. oxygen leakage and temperature are optimum.
Corrosion is usually most severe on the interstage walls and often one wall is
much more attacked than the other.
Corrosion product is usually black magnetic oxide, Fe3O4.
The corrosion product is separated from the metal by a void. In case the disturbed
sheets of corrosion products several mm in thickness fall away, an even metal
surface is left behind.
In some plants, blockage of demisters by corrosion products has caused plant
shut down.



4.2 The major causes of the corrosion damage are:



High velocity of the brine flow affecting floor.
Violent brine flashing (impingement) and collapsing of the flashing vapors
(cavitation) on the walls.
High chloride contents of brine.
High Cu content of recirculating brine.




1 Abstract
The operational experience on the first generation of large MSF desalination plant has demonstrated
that the original expected life of these units has been largely exceeded. Several contracts for the
rehabilitation and upgrading of desalination units installed 20 years ago have been recently awarded,
aiming at extending the life of these units by a further 15 years. Developments in materials technology
have resulted in the adoption of nobler materials, and it is expected that the second generation of large
MSF desalination plants installed in the last 10 years will last for more than 30 years with minimum
maintenance and minor overhauling. On this basis, it is assumed that a 40- to 50-year design life is a
reasonable target which can be obtained if the material selection is optimized in respect of the
operating conditions. The gradual emergence of the MED process in the market portion previously
belonging to MSF technology suggests that an evaluation of the operating conditions and material
selection for MED plants can also grant an expected life of 50 years. The sharp influence of material
selection on plant cost has previously been demonstrated; therefore, the choice of “where” and “how”
to invest in upgrading materials and the evaluation of the financial revenue, in term of extension of
plant life and reduction of maintenance, are key technical aspects for the future of desalination. By
comparing the various operating conditions occurring in the desalination units and the impact on
corrosion/erosion of the materials used, this paper aims at giving guidelines that will allow material
selection to be optimized with respect to the plant costs.1



5 Historical review
The first generation of desalination plants installed in the Gulf from the 1960s through the 1980s use
mainly carbon steel as a material for the evaporator shell and internals. Carbon steel is relatively
inexpensive, readily available and possesses engineering properties that have been understood and
used for decades. Another feature of carbon steel that is largely understood is its tendency to corrode,
and allowance has been made for this in the past by increasing the thickness and hence the weight of
the components that are subject to a corrosive environment. Some significant changes have occurred in
the material selection specified for the second generation of desalination plants designed and
constructed one decade later due to the deeper understanding of the operating conditions occurring
inside the evaporator and their consequences on the material selected. Some of the most significant
changes are summarized in Table 1.




1
    http://www.desline.com/articoli/4071.pdf
Table 1Change in material specifications and operational experience

Component                First-generation         Second-generation     Reasons
                         specification            specification
Vent baffles             Carbon steel             Stainless steel       Understanding of
                                                  Typically AISI 316L   corrosion induced by
                                                                        high
                                                                        concentration of CO2,
                                                                        O2 bromamine and
                                                                        incondensable gases
Support plates           Carbon steel             Stainless steel       Ditto
                                                  Typical AISI 316L
Deaerator                Carbon steel             Stainless steel       Understanding of
                                                  Typical               corrosion induced by
                                                  AISI 317 LN           high
                                                                        oxygen and
                                                                        chloramine
                                                                        concentration
Shell                    Carbon steel painted     Stainless steel       Maintenance
                                                  AISI 316L             reduction
                                                                        Cost effect
Internals                Carbon steel painted     Stainless steel       Ditto
                                                  AISI 316L
Make-up spray            Carbon steel             Duplex steel          Understanding of the
pipe                     Stainless steel          DIN 1.4462            erosion phenomena
                                                                        induced by flashing
                                                                        inside the pipe

The development of stainless steels continues as an understanding of corrosion mechanisms and the
associated kinetics is gained. This has resulted in a wide range of alloys under th umbrella title of
“stainless steels” being readily available. Specific grades of stainless steel may now be applied to counter
particular types of corrosion and/or erosion. Development of corrosion-resistant materials, however, is
not confined to stainless steel. A notable material finding application, particularly for tubing, is titanium.
The erosion and corrosion resistance of titanium is well known in the power industry, and its application
to desalination has resulted in significant reduction in tube weights as a thinner wall thickness is used
for what is already a lighter material than steel.




6 Operational experience analysis
The corrosion mechanism for carbon steel that is most often encountered in desalination plants is that
of general corrosion, whereby metal is removed from the surface of the exposed material, resulting in a
general thinning. This is not the case with stainless steel where corrosion usually takes the form of
pitting. This results in very little metal loss but raises the possibility of localized penetration. Much of the
development of stainless steel is associated with establishing resistance to pitting in high chloride
environments. The adoption of stainless steel instead of carbon steel for evaporator and de-aerator
shell has caused, along with a general upgrading of the material, a reduction in the weights of the

Evaporator, which is indicated in Fig. 1.

Figure 2 Overall weight against capacity




It is difficult, however, to distinguish between the contribution given to the weight reduction by the
adoption of stainless steel and the elimination of corrosion allowances and the refinement in the
structural design which permits lower thickness. The engineering properties of the selected materials
could also result in design changes, for instance tube support spacing.

As can be seen from the graph indicated in Fig. 2
Figure 3Installation cost trend line during the last two decades.




The price per installed gallon has decreased drastically in the last two decades, largely as a result of
economy of scale as unit outputs have increased significantly. However, over this period upgrading of
material selection has also taken place, and market prices have not been substantially affected. As with
all commodities, the unit price tends to fall with increased production and it would be expected that
costs will fall if the demand for the materials Increases. Also in this regard its is difficult to evaluate the
contribution to the price reduction given by

the enhanced commercial competition or by the decrease in the cost of stainless steel; in any case

the second generation of desalination plants is expected to achieve a lifetime of 40 years with

minor overhauling. Maintenance and overhauling of the desalination units also largely benefit from the
adoption of stainless steel material, solid or clad for the evaporator shell. In particular, long and delicate

overhauling periods for touch-up or restoration of the paint in the evaporator stages can be actually

avoided as indicated in Table 2.
Table 2Comparison of first and second generations of MSF

                                         First generation               Second generation
                                         Carbon steel shell             Stainless
                                         painted                        steel shell
Overhauling time                         Long overhauling at            Routine
requested                                frequent intervals
Type of action                           Blasting, patch-work,          Routine
required                                 priming and coating
Cost involved                            High                           Routine


                                                                    Figure 4Effects of corrosion from hydrocarbons and
The possible causes for shortening the life of this generation of
plant or imposing heavy rehabilitation work lie in unforeseen
events such as erosion or impingement caused by debris or
foreign matters and in the presence of highly corrosive
components in the raw seawater as a result of pollution or
accidents.

Figs. 3 show the effect of tube-plate damage due to
impingement by debris and corrosion by hydrocarbons.

Only proper plant monitoring and operation can avoid these
kinds of incidents. Further investment in material upgrading
would not result in additional plant security or longevity.
7 Development of the technology and future prospects
Further development of the material selection for MSF plants is related to the recent developments
in the process thermodynamics and the economic competition with MED, which is the emerging process
in the market. The MED process, in fact, allows a higher heat-exchange coefficient than MSF, and
consequently the heat exchange surface and the weight of this kind of evaporator are lower than for MSF.

Furthermore, different from MSF where the process pattern and thermodynamics did not substantially
changeover in the last 10 years, the MED process has room for further improving efficiency and reducing
costs by increasing operating temperature (still set at very low levels) and modifying operational patterns.
Different operating conditions and process configurations result in a drastically different material
selection. Table 3 indicates the main differences of material selection as well as in the operating
conditions between the two processes. The different types of material can be, in part, related to the
different operating conditions in the plant. In this respect Table 4 summarizes the main differences.

Table 3Comparison of MED and MSF material selection

                             Typical material selection     Typical material selection
                             for MED plants                 for MSF plants
Exchange tubes               Titanium ASTM B338 Gr.         Copper nickel 90/10 or
                             2;first 3 rows                 66/30 high- temp.stages,
                             Al brass remaining rows        heat recovery section
                                                            Al brass, low-temp. stages,
                                                            heat recovery
                                                            Section 66/30or titanium for
                                                            heat rejection section
Tube plates                  Stainless steel AISI 316 L     Solid CuNi 90 /10 or
                                                            aluminum nickel bronze
Shell                        Stainless steel AISI 316 L     Solid or clad stainless steel
Water boxes                  Not applicable                 Carbon steel Cu Ni 90 /10
                                                            clad
Steam boxes                  Stainless steel                Not applicable

Table 4Comparison of MSF and MED operating conditions

                                        MED plant                                MSF plant
Temperature                             Max 65°C                                 Up to 114°C
Oxygen content Chloroamine and          Up to 600 ppb in high-temp. stages       Less than 50 ppb
bromoamine                              Possible because deareation takes        With proper deareation bromoamine
presence                                place in the                             is released from deareator
                                        first stage and due to ejecto-           to vent condenser
                                        compression
Acid cleaning                           Frequent                                 Rare



The reason for the quite high oxygen concentration in the MED process arises from the fact
that no separate deareation takes place and the oxygen is released in the first stages. The concentration of
the oxygen dissolved in the evaporating brine inside the MED shell is governed by Henry’s law, and it
tends to be in equilibrium with the oxygen pressure in the vapour side. The area surrounding the spray
nozzles can be considered as a flashing zone where flashing takes place as a result of a sudden pressure
difference. The oxygen concentration in the seawater at the spray nozzle entrance is in the range of 6 to 8
ppm, depending on the raw seawater temperature. The more the flashing and evaporating brine flows
towards the bottom of the tube bundle, the more the oxygen concentration approaches the
equilibrium value. The vapour generated on the tube bundle acts as stripping steam for the makeup water
while the tube bundle provides a large, interfacial surface between the evaporating liquid and the gas so
that the equilibrium conditions are gradually reached on the bottom of the tube bundle. However, it is
likely that the superior parts of the MED shell and tube bundle, far from equilibrium, are subject to
oxygen concentration

in excess of 600 ppb. Fig. 4 shows the typical oxygen distribution in a multiple effect. The oxygen
distribution differs from stage to stage because each stage has a different operating temperature and
therefore a different Henry’s coefficient for oxygen concentration. The operational experience in several
MSF desalination plants in the Gulf area has proven that the poor deareation and improper venting,
resulting in the accumulation of stagnant pockets of oxygen underneath the vent channel, have
been the reason for tube failure due to corrosion and excessive thinning, especially in the first
stages. Another area subject to pitting corrosion is the upper area in MSF deareator where a
moisture condensate rich in oxygen flows along the walls causing corrosion. Transferring this
experience from MSF to MED, it appears that the venting baffles as well as the upper shell and tube
bundle of MED plant could suffer from corrosion. Furthermore, hydrazine or similar ammonia
compounds inside the effect entrained inside the shell through the motive steam for the ejecto-compressor
can produce ammonia, which can stress corrosion crack the aluminium brass for the tube bundle. In
general, the low temperature and the adoption of titanium in the upper rows would prevent the risk of
stress corrosion cracking the aluminum brass tube to which they are subject in
the presence of ammonia-producing compounds. The adoption of titanium for all tube bundles or
titanium plate exchangers, which are currently used in the market, would completely solve the
problem of stress-corrosion cracking.

Figure 5 Typical oxygen distribution in a multiple effect
Oxygen concentration in excess of 500 ppb is a risk for pitting and stress corrosion cracking, which could
be reduced by the adoption of higher grade stainless steel such as DIN 1.4462 or 254 AVESTA. The
adoption of higher grades of stainless steel could possibly be an alternative to improve the quality of the
material selected for MED desalination plants and maintain costs at the desired levels. Cost reduction can
be achieved in this case by reducing the shell wall thickness thanks to the higher yield strength of duplex
steel. Fig. 5 shows the expected desalination plant weight against the production for a 2.5–5migd plant for
MSF and MED options with a conventional stainless-steel solution and a duplex-steel
Solution.

Figure 6 Weight comparison of MED and MSF desalination plants with 316L or duplex steel.
8 Corrosion in desalination plant

8.1 Typ2e of corrosion

8.1.1      Cavitations and Impingement
Cavitation occurs when a fluid's operational pressure drops below it's vapor pressure causing gas
pockets and bubbles to form and collapse. This can occur in what can be a rather explosive and dramatic
fashion. In fact, this can actually produce steam at the suction of a pump in a matter of minutes. When a
process fluid is supposed to be water in the 20-35°C range, this is entirely unacceptable. Additionally,
this condition can form an airlock, which prevents any incoming fluid from offering cooling effects,
further exacerbating the problem. The locations where this is most likely to occur, such as:

          At the suction of a pump, especially if operating near the net positive suction head required
           (NPSHR)
          At the discharge of a valve or regulator, especially when operating in a near-closed position
          At other geometry-affected flow areas such as pipe elbows and expansions
          Also, by processes incurring sudden expansion, which can lead to dramatic pressure drops

This form of corrosion will eat out the volutes and impellers of centrifugal pumps with ultrapure water
as the fluid. It will eat valve seats. It will contribute to other forms of erosion corrosion, such as found in
elbows and tees. Cavitation should be designed out by reducing hydrodynamic pressure gradients and
designing to avoid pressure drops below the vapor pressure of the liquid and air ingress. The use of
resilient coatings and cathodic protection can also be considered as supplementary control methods.

Figure illustrate picture for cavitations dentition on pump casing




2
    http://corrosion-doctors.org/Forms-cavitation/cavitation.htm
Figure 7Cavitation corrosion of a deaerator




8.1.2      Crevice Corrosion3
Crevice corrosion is a localized form of corrosion usually associated with a stagnant solution on the
micro-environmental level. Such stagnant microenvironments tend to occur in crevices (shielded areas)
such as those formed under gaskets, washers, insulation material, fastener heads, surface deposits,
disbonded coatings, threads, lap joints and clamps. Crevice corrosion is initiated by changes in local
chemistry within the crevice:

      a.   Depletion of inhibitor in the crevice
      b.   Depletion of oxygen in the crevice
      c.   A shift to acid conditions in the crevice
      d.   Build-up of aggressive ion species (e.g. chloride) in the crevice




3
    http://corrosion-doctors.org/Forms-crevice/Crevice.htm
Figure 8Full blown crevice in an otherwise very seawater resistant material.




As oxygen diffusion into the crevice is restricted, a differential aeration cell tends to be set up
between crevice (microenvironment) and the external surface (bulk environment). The
chronology of the aggravating factors leading to a full blown crevice is illustrated here. The
cathodic oxygen reduction reaction cannot be sustained in the crevice area, giving it an anodic character
in the concentration cell. This anodic imbalance can lead to the creation of highly corrosive micro-
environmental conditions in the crevice, conducive to further metal dissolution. This results in the
formation of an acidic micro-environment, together with a high chloride ion concentration.

8.1.3      Erosion Corrosion4




                                     8.2
Erosion corrosion is acceleration in the rate of corrosion attack in metal due to the relative motion of a
corrosive fluid and a metal surface. The increased turbulence caused by pitting on the internal surfaces
of a tube can result in rapidly increasing erosion rates and eventually a leak. Erosion corrosion can also
be aggravated by faulty workmanship. For example, burrs left at cut tube ends can upset smooth water
flow, cause localized turbulence and high flow velocities, resulting in erosion corrosion. A combination
of erosion and corrosion can lead to extremely high pitting rates

4
    http://corrosion-doctors.org/Forms-Erosion/erosion.htm
8.2.1      Environmental Cracking5
Environmental cracking refers to a corrosion cracking caused by a combination of conditions that can
specifically result in one of the following form of corrosion damage:

          Stress Corrosion Cracking (SCC)
          Corrosion fatigue
          Hydrogen embrittlement

Stresses that cause environmental cracking arise from residual cold work, welding, grinding,
thermal treatment, or may be externally applied during service and, to be effective, must be
tensile (as opposed to compressive).

          Stress definition or stress variables
               o Mean stress
               o Maximum stress
               o Minimum stress
               o Constant load/constant strain
               o Strain rate
               o Plane stress/plane strain
               o Modes I, II, or III
               o Biaxial
               o Cyclic frequency
               o Wave shape
          Stress origin
               o Intentional
               o Residual
                       Shearing, punching, cutting
                       Bending, crimping, riveting
                       Welding
                       Machining
                       Grinding
               o Produced by reacted products
               o Applied
                       Quenching
                       Thermal cycling
                       Thermal expansion
                       Vibration
                       Rotation
                       Bolting
                       Dead load
                       Pressure




5
    http://corrosion-doctors.org/Forms-EC/stresses.htm
9 Copper alloy

9.1 Introduction
Copper, the most noble of the metals in common use, has excellent resistance to corrosion in the

atmosphere and in fresh water. In sea-water, the copper nickel alloys have superior resistance to

corrosion coupled with excellent anti-fouling properties. Copper cladding of wooden hulled warships,
introduced by the Royal Navy in the 18th century to prevent damage by wood-boring insects and worms
such as the teredo, was discovered to prevent biofouling by weed and molluscs. This meant that ships
could stay at sea for long periods without cleaning. Nelson’s successful blockade tactics and subsequent
victory at Trafalgar was partly due to the superior speed of his clean-hulled ship. The addition of nickel
to copper improves its strength and durability and also the resistance to corrosion, erosion and
cavitation in all natural waters including sea-water and brackish, treated or polluted waters. The alloys
also show excellent resistance to stress-corrosion cracking and corrosion fatigue. The added advantage
of resistance to bio-fouling, gives a material ideal for application in marine and chemical environments
for ship and boat hulls, desalination plant, heat exchange equipment, sea-water and hydraulic pipelines,
oil rigs and platforms, fish farming cages, sea-water intake screens, etc. The purpose of this publication
is to discuss typical applications for copper-nickel alloys and the reasons for their selection. The two
main alloys contain either 10 or 30% nickel, with iron and manganese additions as shown in Table 12,
which lists typical international and national standards to which the materials may be ordered in
wrought and cast forms.

9.1.1   Specifications, Properties and Availability
The copper-nickel alloys are single phased throughout the full range of compositions and many

standard alloys exist within this range, usually with small additions of other elements for special

purposes. The two most popular of the copper rich alloys contain 10 or 30% of nickel. Some manganese
is invariably present in the commercial alloys as a deoxidant and desulphurizer; it improves working
characteristics and additionally contributes to corrosion resistance in seawater. Other elements which
may be present singly or in combination are:

Iron, added (up to about 2% ) to the alloys required for marine applications. It confers

resistance to impingement attack by flowing sea-water. The initial development of the optimum
compositions of the copper-nickel-iron alloys in the 1930’s has been described by G. L. Bailey

(see bibliography). This work was to meet naval requirements for improved corrosion-resistant

materials for tubes, condensers and other applications involving contact with sea water.

Throughout the publication the term “copper-nickel” refers in fact to copper-nickel-iron alloys.

Chromium, can be used to replace some of the iron content and at one per cent or more

provides higher strength. It is used in a newly-developed 30% nickel casting alloy (IN-768)*. A

low-chromium 16% nickel wrought alloy (C72200) † has been developed in the USA.

Niobium, can be used as a hardening element in cast versions of both the 10% and 30% nickel

alloys (in place of chromium). It also improves weldability of the cast alloys.

Silicon, improves the casting characteristics of the copper-nickel alloys and is used in

conjunction with either chromium or niobium.

* INCO Designation


Tin confers an improved resistance to atmospheric tarnishing and at the 2% level is used with

9% nickel to produce the alloy C72500 †. This has useful spring properties and is used in the

electronics industry. It is not recommended for marine applications.
Table 1 – Application Standards for various Wrought and Cast Products

Table 5 Application Standards for various Wrought and Cast Products




Table 2 – Availability of Wrought Copper-Nickel Alloys

Table 6 Availability of Wrought Copper-Nickel Alloys




Table 7 90-10 copper-nickel-iron alloy. Mechanical properties
9.1.2   Resistance to Corrosion and Bio-Fouling
The 90/10 and 70/30 alloys have excellent resistance to sea-water corrosion and bio-fouling

with some variations in the performance of the alloys under different conditions as shown in

Table 5 and Table 6, for instance, the 90/10 alloy has the better bio-fouling resistance. In Table

5 the corrosion resistance of the 90/10 and 70/30 alloys in heat exchangers and condensers is

compared and in Table 6 the relative resistance of various alloys to fouling in quiet sea-water. If

water velocity is accelerated above 1 m/sec, any slight bio-fouling on metal with good fouling

resistance will be easily detached and swept away. On a material that does not have this good

fouling resistance, strongly adherent, marine organisms would continue to thrive and multiply.

The effect of water velocity on fouling and corrosion rates of various metals is shown in Fig. 1

which also shows the typical service design speeds for certain items of common equipment in

contact with sea-water. The excellent corrosion resistance of 70/30 and 90/10 copper nickel

alloys and their suitability for many applications can be seen. Some materials with apparently

better corrosion resistance may have disadvantages such as lack of resistance to bio-fouling,

lack of availability in the forms required, or susceptibility to crevice corrosion. They may also

be more expensive and therefore less cost-effective over the required service lifetime.

Crevice corrosion can occur in components in sea-water when they are locally starved of oxygen

at a joint or under attached bio-fouling. Table 7 shows the good tolerance of the copper-nickel

alloys to this type of attack, giving these alloys advantages over other materials of equal

corrosion resistance.
The copper-nickel alloys have good corrosion resistance in the quiescent or stagnant conditions

which may occur during the commissioning or overhaul of plant. Where plant is not being used

at design speeds some other materials may fail.

The corrosion resistance of the alloys is due to the protective surface film formed when in

contact with water. On initial immersion cuprous oxide is formed but complex changes occur in

sea water which research work is only now beginning to elucidate. At a flow rate of 0.6 m/s the

equilibrium corrosion rate is an almost negligible 0.002 mm/year. Normally, design flow rates

of up to 3.5 m/s give a satisfactory safety factor for use in pipework systems. This figure makes

allowance for the fact that local speeds may be higher at changes of direction, points of

divergence, etc. If water velocity is excessive, it can cause vortices leading to impingement

attack which can cause premature failure. Where surfaces in contact with water allow smooth

flow, as in ships hulls, different design criteria apply.

As mentioned, the fouling resistance is due to the copper ions at the surface, making it

inhospitable to most marine organisms in slowly moving water. In static conditions there may be

some deposition of chemical salts and biological slimes, possibly leading to some weakly

adherent fouling but such residues are easily detached from the metal’s corrosion resistant

surface, exposing a fresh, biocidally active surface.

When first brought into use, care must be taken to allow copper-nickel alloys to form their

protective corrosion resistant surface freely. Normally, this protective film will develop in six to

eight weeks. Contact with other less noble metals or with cathodic protection systems must be

avoided to ensure development of the corrosion resistant surface film and the non-fouling

properties.
Copper-nickel alloys do not suffer the stress-corrosion problems associated with some other

materials.




Table 8 Comparison or corrosion behaviour of CuNi10Fe and CuNi30Fe in seawater

Environmental                                                      Type of       Service experience
conditions
                                        corrosion
                                                                                 CuNi10Fe             CuNi30Fe
Clean seawater at                                 Uniform, general                      0.0025-              0.0025-
velocities up to 1 m/s                                                                                0.025 mm/a
                                                                                 0.025 mm/a
Clean seawater at                                Impingement attack              Satisfactory         Satisfactory
velocities up to 3.5 m/s *
Polluted seawater                       Accelerated general                      Less resistant       Preferred but not
                                        and pitting                                                       immune
Entrained sand in seawater              Accelerated general                      Unsuitable,               Use
                                        and erosion                              exceptin             CuNi30Fe2Mn2
                                                                                 mild conditions
Accumulated deposits on                 Local attack                             Generally good       Tendency to pit
surface
Hot spots due to local                  Local attack by                          Good                 Good but some
overheating                             denickelification                                             failures
                                                                                                      in extreme
                                                                                                      conditions
Corrosion plus stress                            Stress corrosion                Very resistant       Very resistant
(Vapour side conditions)

Feedwater heaters working               Exfoliation attack                       Resistant            Susceptible
under cyclic conditions
Non-condensable gases †                 Local attack and                         Highly Resistant      Most resistant
                                        general thinning
Hydrogen sulphide in                    General attack                           Less Resistant       Less Resistant
desalination plant
* Local velocities caused by obstructions can be very high.
† lf concentration of CO2 is extremely high, stainless steel may be better cholce.
‡ Attack will increase in concentration or temperature.

Table 6 – Fouling resistance of various alloys in quiet seawater
Arbitrary Rating Scale of
Fouling Resistance
90-100                                                   Best                      Copper90/10 copper-nickel alloy
70-90                                   Good                                              Brass and bronze
50                                      Fair                                     70/30 copper-nickel alloy,
                                                                                 aluminium bronzes,
                                                                                 zinc
10                                      Very Slight                              Nickel-copper alloy 400
0   Least                                  Carbon and low alloy steels,
                                                                                stainless steels,
                                                                                nickel-chromium-high molybdenum
                                                                                alloys
                                                                                               Titanium

Above 1 m/s (about 3 ft/sec or 1.8 knots) most fouling organisms have increasing difficulty in attaching
themselves and clinging to the surface unless already securely attached.
(INCO)




9.1.3    Sea Water Intakes
Sea water is frequently required in large quantities for cooling purposes. One of the problems
associated with sea water intakes in marine- or land-based installations is the occurrence of
gross marine fouling of the entry. This may be of soft growth, barnacles or bivalves. Not only
can this restrict the water flow but the marine fouling may be detached from time to time and
cause blockages in heat exchangers or severe mechanical damage to pumps and valves.
Injection of chemicals such as chlorine can be effective against marine fouling organisms.
However, additions must be closely controlled to be effective and even so, may have a
detrimental effect on the installation and the environment near the outflow. Storage of bulk
chlorine can also be hazardous. Adequate control is possible during steady-state running
conditions but this becomes difficult during downtime when flow ceases.
An alternative is to make intakes and intake screens of 90/10 copper-nickel which is resistant to
fouling. The intake pipes themselves may be of copper-nickel or large concrete piping may be
internally lined either by casting the concrete round a formed pipe or by attaching sheet inside
pipes by rivets or adhesive.

Figure 9Comparison of zinc anode protected steel
Figure 10Large diameter concrete intake pipe




10 Materials for Heat Exchanger Tubes

10.1 Introduction

Heat exchangers take heat from one fluid and pass it to a second. The fire-tube array of a steam
engine is a heat exchanger, taking heat from the hot combustion gases of the firebox and
transmitting it to the water in the boiler. The network of finned tubes in an air conditioner is a
heat exchanger, taking heat from the air of the room and dumping it into the working fluid of the
conditioner. The radiator in a car performs a similar function. A key element in all heat
exchangers is the tube wall or membrane which separates the two fluids. It is required to transmit
heat and there is frequently a large pressure difference across it.

What are the best materials for making heat exchangers? Or, more specifically, what are the best
materials for a conduction-limited exchanger, with substantial pressure difference between the
two fluids?
Figure 1 Schematic of a heat exchanger

10.2 Design Requirements

FUNCTION          Heat Exchanger


OBJECTIVE         Maximise heat flow per unit area, or per unit weight


CONSTRAINTS (a) Support pressure difference p

                  (b) Withstand chloride ions
                  (c) Operating temperature up to 150°C
                  (d) Low Cost



10.2.1.1 Table 1



10.3 The Model
First, a little background on heat flow. Heat transfer from one fluid, through a membrane to a second
fluid, involves convective transfer from fluid 1 into the tube wall, conduction through the wall, and
convection again to transfer it into fluid 2. The heat flux q into the tube wall by convection (in units of
W/m2) is described by the heat transfer equation:


            (1)
in which h1 is the heat transfer coefficient and T1 is the temperature drop across the surface
from fluid 1 into the wall. Conduction is described by the conduction (or Fourier) equation



             (2)

where  is the thermal conductivity of the wall (thickness t) and T12 is the temperature
difference across it.

It is helpful to think of the thermal resistance at surface 1 as 1/h1; that of surface 2 is 1/h2; and
that of the wall itself is t/. Then continuity of heat flux requires that the total resistance 1/U is



                   (3)

where U is called the 'total heat transfer coefficient '. The heat flux from fluid 1 to fluid 2 is then
given by


          (4)

where T is the difference in temperature between the two working fluids. When one of the
fluids is a gas, as in an air conditioner, heat transfer at the tube surface contributes most of the
resistance; then fins are used to increase the surface area across which heat can be transferred.
But when both working fluids are liquid, convective heat transfer is rapid and conduction
through the wall dominates the thermal resistance. In this case simple tube elements are used,
with their wall as thin as possible to maximise /t. We will consider the second case: conduction
limited heat transfer. Then 1/h1 and 1/h2 are negligible when compared with t/, and the heat
transfer equation becomes


          (5)

Consider, now, a heat exchanger with many tubes, each of radius r and wall thickness t with a
pressure difference p between the inside and outside. Our aim is to select a material to
maximise the total heat flow, while safely carrying the pressure difference p. The total heat
flow is



                   (6)

where A is the total surface area of tubing.
This is the objective function. The constraint is that the wall thickness must be sufficient to
support the pressure difference p. This requires that the stress in the wall remain below the
elastic limit (yield strength) el (times a safety factor, which need not be included in this
analysis):



                  (7)

Eliminating t between the last two equations gives


                    (8)

The heat flow per unit area of tube wall, Q/A, is maximised by maximising the performance
index:

            (9)

Four further considerations enter the selection. It is essential to choose a material that withstands
corrosion in the working fluids, which we take here to be water containing chloride ions (sea
water). Cost will naturally be of concern. The maximum service temperature must be adequate
and the material should be available as drawn tube.

10.4 The Selection
A preliminary selection using the Generic filter is shown in Figures 2-4. The first chart is of elastic limit
versus thermal conductivity, to allow us to maximise the value of M1. The second stage shows maximum
service temperature plotted as a bar-chart against resistance to sea-water, selecting materials with high
temperature resistance and high resistance to corrosion in sea-water. The last stage shows a bar chart of
material cost against available forms, selecting cheap materials that are available as sheet or tube.
Figure 2 A Chart of Elastic Limit versus Thermal Conductivity




Figure 3 A Bar-chart of Maximum Service Temperature versus Resistance to Sea-Water
Corrosion
Figure 4 Material Cost against Available Forms

The results of this selection are shown in Results Table 1, and they suggest that it may be worth
transferring the selection criteria to the coppers database to refine the search for a suitable
material.

10.5 Results

    Material (ranked by M1)                                      Comment


                                    Have the best performance index, but relatively poor corrosion
High Conductivity Coppers
                                    resistance


Brasses                             Again, relatively poor corrosion resistance


Wrought Martensitic Stainless
                                    A good choice, but steel is more dense than copper
Steel


Aluminium Bronzes                   An economical and practical choice
10.5.1.1 Table 1 The Results of the Selection using the Generic Filter

            Material (ranked by M1)                                      Comment


90/10 Aluminium bronze, cold wkd (wrought)        The aluminium bronzes are cheap


92/8 Aluminium bronze, hard (wrought)


93/7 Aluminium bronze, hard (wrought)


95/5 Aluminium bronze, 1/2 hard (wrought)


95/5 Aluminium bronze, hard (wrought)


Nickel iron aluminium bronze, as extruded         The Nickel iron aluminium bronzes are more corrosion
(wrought)                                         resistant


Nickel iron aluminium bronze, hot wkd
(wrought)



10.5.1.2 Table 2 The Results of the Selection by expanding the coppers branch

10.6 PostScript
Conduction may limit heat flow in theory, but unspeakable things go on inside heat exchangers. Sea
water—often one of the working fluids—seethes with biofouling organisms which attach themselves to
tube walls and thrive, creating a layer of high thermal resistance and impeding fluid flow, like barnacles
on a boat. Some materials are more resistant to biofouling than others; copper-nickel alloys are
particularly good, probably because the organisms dislike copper salts, even in very low concentrations.
Otherwise the problem must be tackled by adding chemical inhibitors to the fluids, or by scraping—the
traditional winter pass-time of boat owners.


It is sometimes important to minimise the weight of heat exchangers. Repeating the calculation
to seek materials for the lightest heat exchanger gives, instead of M, the index:
(10)

where  is the density of the materials from which the tubes are made. This is quite a different
index—the strength varies to the power 2 because the weight depends on the wall thickness, and
from Eqn 7 we know that wall thickness varies as 1/strength.

Of course, all copper alloys have roughly the same density, so there is little point applying this
index within the coppers in the database—but if copper alloys were compared with stainless
steels at the Generic level, then it would be relevant.




11 Materials in Seawater Reverse Osmosis (SWRO) Plants6
In SWRO plants the operating environments are much less severe than in MSF plants. For
example, the operating temperatures are much lower (below 50o C and non-condensable gases
(e.g. CO2 , O2 , H2S NH3, Br2 etc) are not involved during seawater conversion. Austenitic
stainless steels are the conventional materials used for high pressure piping leading to RO
membrane module, brine rejection pipe, product water outlet pipe and high pressure pumps. In
SWRO plants, high velocities of the feed water and design do not encourage crevice formation.
However, high pressure pipings (close to weld or heat affected zone) headers, connectors,
flanges, seals of pumps and membrane containment vessels are prone to crevice corrosion
attack in case stagnant conditions are developed or deposits are formed in the piping
system due to operational problems. The performance of materials in different
SWRO plants is given in Table 4.




6

http://www.swcc.gov.sa/files/assets/Research/Technical%20Papers/Corrosion/RELEVANCE%20OF%20CORROSION
%20RESEARCH%20IN%20THE%20MATERIALSELECTION%20FOR.pdf
11.1 Use of Superior Materials

11.1.1 Flash Chambers
The use of stainless steel cladding or Cu/Ni cladding on mild steel in all the stages or
in the first few stages and that of bare CS in the remaining stages appear to work very
well in evaporators of the desalination plants. Keeping in view the existing materials,
the evaporators are designed with a high corrosion allowance therefore, the chambers
are not much affected by general or uniform corrosion. However, localized corrosion
problems are quite frequent and troublesome and are the cause of concern
During shut down, slow moving or stagnant high chloride brine, crevices (formed
by salt and by scaling) and D.O. produce most favourable environment for initiating
and propagating corrosion process. Use of high alloy stainless steels, Ni-base alloys
or titanium as construction materials could perhaps be the ideal solution to avoid corrosion
in flash chambers. Even considering these materials as the best proposition
for long term trouble free operational life of the plant, the exorbitant cost would not
permit their use as constructional material.
Use of cement-concrete as construction material appears to be quite promising
due to its low cost, strength and durability. Erosion-corrosion resistance of the
cementitious material under conditions of high flow corrosive brine and thermal
stresses and airtightness of the structures are the problems which are to be looked
into.
11.1.2 Heat Exchangers
The predominant cause of the failure of heat exchanger tubes is circulating water
flow conditions resulting in tube inlet erosion/corrosion. This tube inlet damage is
almost located in the first 150 mm of the tube inlets and often results in perforation.


11.1.3 Relevance of Corrosion Research in the Material Selection
Cu-Ni (90/10 or 70/30), modified alloy Cu-Ni-Fe-Mn (66/30/2/2) or Ti are the
materials used for heat exchanger tubes. The choice of the most suitable material
depends upon the system (brine heater, heat recovery or heat rejection) to be considered.
Titanium though costly has replaced Cu/Ni alloys for heat rejection and brine
heater tubes due to its excellent erosion-corrosion resistance and heat transfer
properties. Titanium has the tendency to undergo crevice corrosion specially at high
temperatures. Addition of precious metals to titanium though make it slightly more
expensive but increases its resistance to crevice corrosion tremendously. Alloys like
Ti-0.15pd, Ti-005u-0.05Niand Ti-0.05pd-.3 Cu have excellent resistance towards
crevice corrosion. Tables 5 and 6 provide some physical properties data relevant to
heat transfer tubes including failure rates and cost. Conductive plastic composites
containing high aspect ratio fillers (brasses, Al, Ni-plated mica, stainless steel fibres)
have thermal conductivity many magnitude higher than the case polymer. These
materials could be easier to fabricate, stronger, immune to corrosion and erosion,
possessing good heat transfer properties and should be cheaper than the traditional7
heat exchanger materials.8




11.1.4 Venting System
Conventional materials like CS cladded with SS 304, 316 or Cu-Ni which were previously
employed in ejector body, nozzle and condenser, pipings showed pitting, SCC,
metal loss or erosion, are now replaced by more superior materials like Incoloy 825,
254SM0 or FRP.


7
  Saricimen, H., et al, “Performance of Austenitic StainlessSteels in MSF Desalination
Plant Flash Chambers in the Arabian Gull” Desalination October,
1990.
8
  Malik, A.U., and Kutty, Mayan, A., “Corrosion and Materials Selection in
Desalination Plants” Proc. SWCC Operation and Maintenance Conference,
April 27-29, 1992 p. 304.
11.1.5 Pumps
Discharge columns and diffusers of brine recycle and blow down pumps which are
usually made of Ni-resist showed SCC, fatigue or erosion due to porosity, lack of
stress relieving operation and poor casting. Replacements with more expensive
materials like SS316 or Duplex SS 2205 appear to overcome most of the erosioncorrosion
problems.
11.1.6 Pipings
Cement concrete (CC), reinforced cement concrete (RCC) and prestressed concrete
(PC) which have been conventional material for product water transmission pipe
lines showed frequent failures mainly due to rebar corrosion. The replacement of these materials
with fusion bonded epoxy (FBE) or urethane (FBU) appears to minimize the risk of failure.
Coating of rebars with FBE or FBU is though costlier but provide protection against corrosion.



12 Conclusion


         All in all, you can see that desalination plant has to adapt the nature of the environment.
Environment won’t forgive the material of desalination plant. Therefore, you need to select the material
that can adapt the environment and resist the corrosion. Corrosion is the main part of material selection. It
attacks almost every part of desalination plant. It results from stagnancy, deposition, dealloying, galvanic
couplation, dealloying and vapor space attack. The local attack (pitting, crevice) can be avoided in
most of the cases by minimizing dissolved oxygen level of brine and incondensable gases, proper
flushing and keeping an inert atmosphere during shut down, mechanical or chemical cleaning of
deposits and maintaining C.P.

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Material selection of desalination plants

  • 1. Contents 1 Introduction .......................................................................................................................................... 3 2 Corrosion in desalination plants ........................................................................................................... 3 3 Vapor-Space Corrosion ......................................................................................................................... 3 4 Corrosion in Flash Champers ................................................................................................................ 4 4.1 The interesting features of the corrosion of flash chamber (mild steel) are as follows: .............. 4 4.2 The major causes of the corrosion damage are: .......................................................................... 5 1 Abstract ...................................................................................................................................................... 5 5 Historical review ................................................................................................................................... 6 6 Operational experience analysis ........................................................................................................... 7 7 Development of the technology and future prospects ...................................................................... 11 8 Corrosion in desalination plant ........................................................................................................... 14 8.1 Type of corrosion ........................................................................................................................ 14 8.1.1 Cavitations and Impingement ............................................................................................. 14 8.1.2 Crevice Corrosion ................................................................................................................ 15 8.1.3 Erosion Corrosion ................................................................................................................ 16 8.2 ........................................................................................................................................................... 16 8.2.1 Environmental Cracking ...................................................................................................... 17 9 Copper alloy ........................................................................................................................................ 18 9.1 Introduction ................................................................................................................................ 18 9.1.1 Specifications, Properties and Availability .......................................................................... 18 9.1.2 Resistance to Corrosion and Bio-Fouling ............................................................................ 21 9.1.3 Sea Water Intakes ............................................................................................................... 24 10 Materials for Heat Exchanger Tubes ............................................................................................... 25 10.1 Introduction ................................................................................................................................ 25
  • 2. 10.2 Design Requirements .................................................................................................................. 26 10.3 The Model ................................................................................................................................... 26 10.4 The Selection ............................................................................................................................... 28 10.5 Results ......................................................................................................................................... 30 10.6 PostScript .................................................................................................................................... 31 11 Materials in Seawater Reverse Osmosis (SWRO) Plants ................................................................. 32 11.1 Use of Superior Materials ........................................................................................................... 34 11.1.1 Flash Chambers ................................................................................................................... 34 11.1.2 Heat Exchangers.................................................................................................................. 34 11.1.3 Relevance of Corrosion Research in the Material Selection ............................................... 34 11.1.4 Venting System ................................................................................................................... 35 11.1.5 Pumps.................................................................................................................................. 36 11.1.6 Pipings ................................................................................................................................. 37 12 Conclusion ....................................................................................................................................... 37
  • 3. 1 Introduction To build desalination plant needs a huge study of material metals, composites and non- metals which not just meet the requirements of the design and operation but also to adapt the nature of the environment that surround the plants. One important subject to think about during selecting the proper material for constructing for specific unit or component is corrosion characteristics. Desalination power plant usually exposed to different and varied types of environment such as seawater, seawater-air and salt-air aerosols, corrosive gases, very fast or extremely slow moving liquids, particulates contained in high velocity fluids or deposit-forming liquids all of them create a number of corrosion related problems. 2 Corrosion in desalination plants Seawater desalination plant involve a lot of corrosion because of the operation in environment that doesn’t forgive that consist of seawater, seawater-air and salt-air aerosols, corrosive gases, very fast or slow moving liquids, particulates contained in high velocity fluids or deposit forming liquids. 3 Vapor-Space Corrosion In MSF plants vapor space conditions are less well controlled and severe corrosion has been observed in both acid and additive dosed plants at rates well in excess of the designed corrosion allowance. Apart from water vapor which is always present, incondensable gases evolved from the flashing brine will be present. These gases are mainly CO2, O2, and N2. In some cases H2S and NH3 also would be present if seawater
  • 4. feed to the plant is polluted with decomposing organic materials. 4 Corrosion in Flash Champers Figure 1, Corrosion of a flash chamber (3rd stage). One of the most familiar construction materials for flash chapmers is the carbon steel. It is used as such or cladded with stainless steel or Cu-Ni in early or all the stages. Epoxy coating has also been used. Flash chambers are subjected to severe corrosion and potential metal failures. The role of oxygen in the corrosion of metals of construction in MSF plants in general and evaporators in particular is quite complex. 4.1 The interesting features of the corrosion of flash chamber (mild steel) are as follows: Corrosion is maximum in the middle of the stages where the combined effects of two competing factors e.g. oxygen leakage and temperature are optimum. Corrosion is usually most severe on the interstage walls and often one wall is much more attacked than the other.
  • 5. Corrosion product is usually black magnetic oxide, Fe3O4. The corrosion product is separated from the metal by a void. In case the disturbed sheets of corrosion products several mm in thickness fall away, an even metal surface is left behind. In some plants, blockage of demisters by corrosion products has caused plant shut down. 4.2 The major causes of the corrosion damage are: High velocity of the brine flow affecting floor. Violent brine flashing (impingement) and collapsing of the flashing vapors (cavitation) on the walls. High chloride contents of brine. High Cu content of recirculating brine. 1 Abstract The operational experience on the first generation of large MSF desalination plant has demonstrated that the original expected life of these units has been largely exceeded. Several contracts for the rehabilitation and upgrading of desalination units installed 20 years ago have been recently awarded, aiming at extending the life of these units by a further 15 years. Developments in materials technology have resulted in the adoption of nobler materials, and it is expected that the second generation of large MSF desalination plants installed in the last 10 years will last for more than 30 years with minimum maintenance and minor overhauling. On this basis, it is assumed that a 40- to 50-year design life is a reasonable target which can be obtained if the material selection is optimized in respect of the operating conditions. The gradual emergence of the MED process in the market portion previously belonging to MSF technology suggests that an evaluation of the operating conditions and material
  • 6. selection for MED plants can also grant an expected life of 50 years. The sharp influence of material selection on plant cost has previously been demonstrated; therefore, the choice of “where” and “how” to invest in upgrading materials and the evaluation of the financial revenue, in term of extension of plant life and reduction of maintenance, are key technical aspects for the future of desalination. By comparing the various operating conditions occurring in the desalination units and the impact on corrosion/erosion of the materials used, this paper aims at giving guidelines that will allow material selection to be optimized with respect to the plant costs.1 5 Historical review The first generation of desalination plants installed in the Gulf from the 1960s through the 1980s use mainly carbon steel as a material for the evaporator shell and internals. Carbon steel is relatively inexpensive, readily available and possesses engineering properties that have been understood and used for decades. Another feature of carbon steel that is largely understood is its tendency to corrode, and allowance has been made for this in the past by increasing the thickness and hence the weight of the components that are subject to a corrosive environment. Some significant changes have occurred in the material selection specified for the second generation of desalination plants designed and constructed one decade later due to the deeper understanding of the operating conditions occurring inside the evaporator and their consequences on the material selected. Some of the most significant changes are summarized in Table 1. 1 http://www.desline.com/articoli/4071.pdf
  • 7. Table 1Change in material specifications and operational experience Component First-generation Second-generation Reasons specification specification Vent baffles Carbon steel Stainless steel Understanding of Typically AISI 316L corrosion induced by high concentration of CO2, O2 bromamine and incondensable gases Support plates Carbon steel Stainless steel Ditto Typical AISI 316L Deaerator Carbon steel Stainless steel Understanding of Typical corrosion induced by AISI 317 LN high oxygen and chloramine concentration Shell Carbon steel painted Stainless steel Maintenance AISI 316L reduction Cost effect Internals Carbon steel painted Stainless steel Ditto AISI 316L Make-up spray Carbon steel Duplex steel Understanding of the pipe Stainless steel DIN 1.4462 erosion phenomena induced by flashing inside the pipe The development of stainless steels continues as an understanding of corrosion mechanisms and the associated kinetics is gained. This has resulted in a wide range of alloys under th umbrella title of “stainless steels” being readily available. Specific grades of stainless steel may now be applied to counter particular types of corrosion and/or erosion. Development of corrosion-resistant materials, however, is not confined to stainless steel. A notable material finding application, particularly for tubing, is titanium. The erosion and corrosion resistance of titanium is well known in the power industry, and its application to desalination has resulted in significant reduction in tube weights as a thinner wall thickness is used for what is already a lighter material than steel. 6 Operational experience analysis The corrosion mechanism for carbon steel that is most often encountered in desalination plants is that of general corrosion, whereby metal is removed from the surface of the exposed material, resulting in a general thinning. This is not the case with stainless steel where corrosion usually takes the form of pitting. This results in very little metal loss but raises the possibility of localized penetration. Much of the
  • 8. development of stainless steel is associated with establishing resistance to pitting in high chloride environments. The adoption of stainless steel instead of carbon steel for evaporator and de-aerator shell has caused, along with a general upgrading of the material, a reduction in the weights of the Evaporator, which is indicated in Fig. 1. Figure 2 Overall weight against capacity It is difficult, however, to distinguish between the contribution given to the weight reduction by the adoption of stainless steel and the elimination of corrosion allowances and the refinement in the structural design which permits lower thickness. The engineering properties of the selected materials could also result in design changes, for instance tube support spacing. As can be seen from the graph indicated in Fig. 2
  • 9. Figure 3Installation cost trend line during the last two decades. The price per installed gallon has decreased drastically in the last two decades, largely as a result of economy of scale as unit outputs have increased significantly. However, over this period upgrading of material selection has also taken place, and market prices have not been substantially affected. As with all commodities, the unit price tends to fall with increased production and it would be expected that costs will fall if the demand for the materials Increases. Also in this regard its is difficult to evaluate the contribution to the price reduction given by the enhanced commercial competition or by the decrease in the cost of stainless steel; in any case the second generation of desalination plants is expected to achieve a lifetime of 40 years with minor overhauling. Maintenance and overhauling of the desalination units also largely benefit from the adoption of stainless steel material, solid or clad for the evaporator shell. In particular, long and delicate overhauling periods for touch-up or restoration of the paint in the evaporator stages can be actually avoided as indicated in Table 2.
  • 10. Table 2Comparison of first and second generations of MSF First generation Second generation Carbon steel shell Stainless painted steel shell Overhauling time Long overhauling at Routine requested frequent intervals Type of action Blasting, patch-work, Routine required priming and coating Cost involved High Routine Figure 4Effects of corrosion from hydrocarbons and The possible causes for shortening the life of this generation of plant or imposing heavy rehabilitation work lie in unforeseen events such as erosion or impingement caused by debris or foreign matters and in the presence of highly corrosive components in the raw seawater as a result of pollution or accidents. Figs. 3 show the effect of tube-plate damage due to impingement by debris and corrosion by hydrocarbons. Only proper plant monitoring and operation can avoid these kinds of incidents. Further investment in material upgrading would not result in additional plant security or longevity.
  • 11. 7 Development of the technology and future prospects Further development of the material selection for MSF plants is related to the recent developments in the process thermodynamics and the economic competition with MED, which is the emerging process in the market. The MED process, in fact, allows a higher heat-exchange coefficient than MSF, and consequently the heat exchange surface and the weight of this kind of evaporator are lower than for MSF. Furthermore, different from MSF where the process pattern and thermodynamics did not substantially changeover in the last 10 years, the MED process has room for further improving efficiency and reducing costs by increasing operating temperature (still set at very low levels) and modifying operational patterns. Different operating conditions and process configurations result in a drastically different material selection. Table 3 indicates the main differences of material selection as well as in the operating conditions between the two processes. The different types of material can be, in part, related to the different operating conditions in the plant. In this respect Table 4 summarizes the main differences. Table 3Comparison of MED and MSF material selection Typical material selection Typical material selection for MED plants for MSF plants Exchange tubes Titanium ASTM B338 Gr. Copper nickel 90/10 or 2;first 3 rows 66/30 high- temp.stages, Al brass remaining rows heat recovery section Al brass, low-temp. stages, heat recovery Section 66/30or titanium for heat rejection section Tube plates Stainless steel AISI 316 L Solid CuNi 90 /10 or aluminum nickel bronze Shell Stainless steel AISI 316 L Solid or clad stainless steel Water boxes Not applicable Carbon steel Cu Ni 90 /10 clad Steam boxes Stainless steel Not applicable Table 4Comparison of MSF and MED operating conditions MED plant MSF plant Temperature Max 65°C Up to 114°C Oxygen content Chloroamine and Up to 600 ppb in high-temp. stages Less than 50 ppb bromoamine Possible because deareation takes With proper deareation bromoamine presence place in the is released from deareator first stage and due to ejecto- to vent condenser compression Acid cleaning Frequent Rare The reason for the quite high oxygen concentration in the MED process arises from the fact that no separate deareation takes place and the oxygen is released in the first stages. The concentration of the oxygen dissolved in the evaporating brine inside the MED shell is governed by Henry’s law, and it tends to be in equilibrium with the oxygen pressure in the vapour side. The area surrounding the spray nozzles can be considered as a flashing zone where flashing takes place as a result of a sudden pressure difference. The oxygen concentration in the seawater at the spray nozzle entrance is in the range of 6 to 8 ppm, depending on the raw seawater temperature. The more the flashing and evaporating brine flows towards the bottom of the tube bundle, the more the oxygen concentration approaches the
  • 12. equilibrium value. The vapour generated on the tube bundle acts as stripping steam for the makeup water while the tube bundle provides a large, interfacial surface between the evaporating liquid and the gas so that the equilibrium conditions are gradually reached on the bottom of the tube bundle. However, it is likely that the superior parts of the MED shell and tube bundle, far from equilibrium, are subject to oxygen concentration in excess of 600 ppb. Fig. 4 shows the typical oxygen distribution in a multiple effect. The oxygen distribution differs from stage to stage because each stage has a different operating temperature and therefore a different Henry’s coefficient for oxygen concentration. The operational experience in several MSF desalination plants in the Gulf area has proven that the poor deareation and improper venting, resulting in the accumulation of stagnant pockets of oxygen underneath the vent channel, have been the reason for tube failure due to corrosion and excessive thinning, especially in the first stages. Another area subject to pitting corrosion is the upper area in MSF deareator where a moisture condensate rich in oxygen flows along the walls causing corrosion. Transferring this experience from MSF to MED, it appears that the venting baffles as well as the upper shell and tube bundle of MED plant could suffer from corrosion. Furthermore, hydrazine or similar ammonia compounds inside the effect entrained inside the shell through the motive steam for the ejecto-compressor can produce ammonia, which can stress corrosion crack the aluminium brass for the tube bundle. In general, the low temperature and the adoption of titanium in the upper rows would prevent the risk of stress corrosion cracking the aluminum brass tube to which they are subject in the presence of ammonia-producing compounds. The adoption of titanium for all tube bundles or titanium plate exchangers, which are currently used in the market, would completely solve the problem of stress-corrosion cracking. Figure 5 Typical oxygen distribution in a multiple effect
  • 13. Oxygen concentration in excess of 500 ppb is a risk for pitting and stress corrosion cracking, which could be reduced by the adoption of higher grade stainless steel such as DIN 1.4462 or 254 AVESTA. The adoption of higher grades of stainless steel could possibly be an alternative to improve the quality of the material selected for MED desalination plants and maintain costs at the desired levels. Cost reduction can be achieved in this case by reducing the shell wall thickness thanks to the higher yield strength of duplex steel. Fig. 5 shows the expected desalination plant weight against the production for a 2.5–5migd plant for MSF and MED options with a conventional stainless-steel solution and a duplex-steel Solution. Figure 6 Weight comparison of MED and MSF desalination plants with 316L or duplex steel.
  • 14. 8 Corrosion in desalination plant 8.1 Typ2e of corrosion 8.1.1 Cavitations and Impingement Cavitation occurs when a fluid's operational pressure drops below it's vapor pressure causing gas pockets and bubbles to form and collapse. This can occur in what can be a rather explosive and dramatic fashion. In fact, this can actually produce steam at the suction of a pump in a matter of minutes. When a process fluid is supposed to be water in the 20-35°C range, this is entirely unacceptable. Additionally, this condition can form an airlock, which prevents any incoming fluid from offering cooling effects, further exacerbating the problem. The locations where this is most likely to occur, such as:  At the suction of a pump, especially if operating near the net positive suction head required (NPSHR)  At the discharge of a valve or regulator, especially when operating in a near-closed position  At other geometry-affected flow areas such as pipe elbows and expansions  Also, by processes incurring sudden expansion, which can lead to dramatic pressure drops This form of corrosion will eat out the volutes and impellers of centrifugal pumps with ultrapure water as the fluid. It will eat valve seats. It will contribute to other forms of erosion corrosion, such as found in elbows and tees. Cavitation should be designed out by reducing hydrodynamic pressure gradients and designing to avoid pressure drops below the vapor pressure of the liquid and air ingress. The use of resilient coatings and cathodic protection can also be considered as supplementary control methods. Figure illustrate picture for cavitations dentition on pump casing 2 http://corrosion-doctors.org/Forms-cavitation/cavitation.htm
  • 15. Figure 7Cavitation corrosion of a deaerator 8.1.2 Crevice Corrosion3 Crevice corrosion is a localized form of corrosion usually associated with a stagnant solution on the micro-environmental level. Such stagnant microenvironments tend to occur in crevices (shielded areas) such as those formed under gaskets, washers, insulation material, fastener heads, surface deposits, disbonded coatings, threads, lap joints and clamps. Crevice corrosion is initiated by changes in local chemistry within the crevice: a. Depletion of inhibitor in the crevice b. Depletion of oxygen in the crevice c. A shift to acid conditions in the crevice d. Build-up of aggressive ion species (e.g. chloride) in the crevice 3 http://corrosion-doctors.org/Forms-crevice/Crevice.htm
  • 16. Figure 8Full blown crevice in an otherwise very seawater resistant material. As oxygen diffusion into the crevice is restricted, a differential aeration cell tends to be set up between crevice (microenvironment) and the external surface (bulk environment). The chronology of the aggravating factors leading to a full blown crevice is illustrated here. The cathodic oxygen reduction reaction cannot be sustained in the crevice area, giving it an anodic character in the concentration cell. This anodic imbalance can lead to the creation of highly corrosive micro- environmental conditions in the crevice, conducive to further metal dissolution. This results in the formation of an acidic micro-environment, together with a high chloride ion concentration. 8.1.3 Erosion Corrosion4 8.2 Erosion corrosion is acceleration in the rate of corrosion attack in metal due to the relative motion of a corrosive fluid and a metal surface. The increased turbulence caused by pitting on the internal surfaces of a tube can result in rapidly increasing erosion rates and eventually a leak. Erosion corrosion can also be aggravated by faulty workmanship. For example, burrs left at cut tube ends can upset smooth water flow, cause localized turbulence and high flow velocities, resulting in erosion corrosion. A combination of erosion and corrosion can lead to extremely high pitting rates 4 http://corrosion-doctors.org/Forms-Erosion/erosion.htm
  • 17. 8.2.1 Environmental Cracking5 Environmental cracking refers to a corrosion cracking caused by a combination of conditions that can specifically result in one of the following form of corrosion damage:  Stress Corrosion Cracking (SCC)  Corrosion fatigue  Hydrogen embrittlement Stresses that cause environmental cracking arise from residual cold work, welding, grinding, thermal treatment, or may be externally applied during service and, to be effective, must be tensile (as opposed to compressive).  Stress definition or stress variables o Mean stress o Maximum stress o Minimum stress o Constant load/constant strain o Strain rate o Plane stress/plane strain o Modes I, II, or III o Biaxial o Cyclic frequency o Wave shape  Stress origin o Intentional o Residual  Shearing, punching, cutting  Bending, crimping, riveting  Welding  Machining  Grinding o Produced by reacted products o Applied  Quenching  Thermal cycling  Thermal expansion  Vibration  Rotation  Bolting  Dead load  Pressure 5 http://corrosion-doctors.org/Forms-EC/stresses.htm
  • 18. 9 Copper alloy 9.1 Introduction Copper, the most noble of the metals in common use, has excellent resistance to corrosion in the atmosphere and in fresh water. In sea-water, the copper nickel alloys have superior resistance to corrosion coupled with excellent anti-fouling properties. Copper cladding of wooden hulled warships, introduced by the Royal Navy in the 18th century to prevent damage by wood-boring insects and worms such as the teredo, was discovered to prevent biofouling by weed and molluscs. This meant that ships could stay at sea for long periods without cleaning. Nelson’s successful blockade tactics and subsequent victory at Trafalgar was partly due to the superior speed of his clean-hulled ship. The addition of nickel to copper improves its strength and durability and also the resistance to corrosion, erosion and cavitation in all natural waters including sea-water and brackish, treated or polluted waters. The alloys also show excellent resistance to stress-corrosion cracking and corrosion fatigue. The added advantage of resistance to bio-fouling, gives a material ideal for application in marine and chemical environments for ship and boat hulls, desalination plant, heat exchange equipment, sea-water and hydraulic pipelines, oil rigs and platforms, fish farming cages, sea-water intake screens, etc. The purpose of this publication is to discuss typical applications for copper-nickel alloys and the reasons for their selection. The two main alloys contain either 10 or 30% nickel, with iron and manganese additions as shown in Table 12, which lists typical international and national standards to which the materials may be ordered in wrought and cast forms. 9.1.1 Specifications, Properties and Availability The copper-nickel alloys are single phased throughout the full range of compositions and many standard alloys exist within this range, usually with small additions of other elements for special purposes. The two most popular of the copper rich alloys contain 10 or 30% of nickel. Some manganese is invariably present in the commercial alloys as a deoxidant and desulphurizer; it improves working characteristics and additionally contributes to corrosion resistance in seawater. Other elements which may be present singly or in combination are: Iron, added (up to about 2% ) to the alloys required for marine applications. It confers resistance to impingement attack by flowing sea-water. The initial development of the optimum
  • 19. compositions of the copper-nickel-iron alloys in the 1930’s has been described by G. L. Bailey (see bibliography). This work was to meet naval requirements for improved corrosion-resistant materials for tubes, condensers and other applications involving contact with sea water. Throughout the publication the term “copper-nickel” refers in fact to copper-nickel-iron alloys. Chromium, can be used to replace some of the iron content and at one per cent or more provides higher strength. It is used in a newly-developed 30% nickel casting alloy (IN-768)*. A low-chromium 16% nickel wrought alloy (C72200) † has been developed in the USA. Niobium, can be used as a hardening element in cast versions of both the 10% and 30% nickel alloys (in place of chromium). It also improves weldability of the cast alloys. Silicon, improves the casting characteristics of the copper-nickel alloys and is used in conjunction with either chromium or niobium. * INCO Designation Tin confers an improved resistance to atmospheric tarnishing and at the 2% level is used with 9% nickel to produce the alloy C72500 †. This has useful spring properties and is used in the electronics industry. It is not recommended for marine applications.
  • 20. Table 1 – Application Standards for various Wrought and Cast Products Table 5 Application Standards for various Wrought and Cast Products Table 2 – Availability of Wrought Copper-Nickel Alloys Table 6 Availability of Wrought Copper-Nickel Alloys Table 7 90-10 copper-nickel-iron alloy. Mechanical properties
  • 21. 9.1.2 Resistance to Corrosion and Bio-Fouling The 90/10 and 70/30 alloys have excellent resistance to sea-water corrosion and bio-fouling with some variations in the performance of the alloys under different conditions as shown in Table 5 and Table 6, for instance, the 90/10 alloy has the better bio-fouling resistance. In Table 5 the corrosion resistance of the 90/10 and 70/30 alloys in heat exchangers and condensers is compared and in Table 6 the relative resistance of various alloys to fouling in quiet sea-water. If water velocity is accelerated above 1 m/sec, any slight bio-fouling on metal with good fouling resistance will be easily detached and swept away. On a material that does not have this good fouling resistance, strongly adherent, marine organisms would continue to thrive and multiply. The effect of water velocity on fouling and corrosion rates of various metals is shown in Fig. 1 which also shows the typical service design speeds for certain items of common equipment in contact with sea-water. The excellent corrosion resistance of 70/30 and 90/10 copper nickel alloys and their suitability for many applications can be seen. Some materials with apparently better corrosion resistance may have disadvantages such as lack of resistance to bio-fouling, lack of availability in the forms required, or susceptibility to crevice corrosion. They may also be more expensive and therefore less cost-effective over the required service lifetime. Crevice corrosion can occur in components in sea-water when they are locally starved of oxygen at a joint or under attached bio-fouling. Table 7 shows the good tolerance of the copper-nickel alloys to this type of attack, giving these alloys advantages over other materials of equal corrosion resistance.
  • 22. The copper-nickel alloys have good corrosion resistance in the quiescent or stagnant conditions which may occur during the commissioning or overhaul of plant. Where plant is not being used at design speeds some other materials may fail. The corrosion resistance of the alloys is due to the protective surface film formed when in contact with water. On initial immersion cuprous oxide is formed but complex changes occur in sea water which research work is only now beginning to elucidate. At a flow rate of 0.6 m/s the equilibrium corrosion rate is an almost negligible 0.002 mm/year. Normally, design flow rates of up to 3.5 m/s give a satisfactory safety factor for use in pipework systems. This figure makes allowance for the fact that local speeds may be higher at changes of direction, points of divergence, etc. If water velocity is excessive, it can cause vortices leading to impingement attack which can cause premature failure. Where surfaces in contact with water allow smooth flow, as in ships hulls, different design criteria apply. As mentioned, the fouling resistance is due to the copper ions at the surface, making it inhospitable to most marine organisms in slowly moving water. In static conditions there may be some deposition of chemical salts and biological slimes, possibly leading to some weakly adherent fouling but such residues are easily detached from the metal’s corrosion resistant surface, exposing a fresh, biocidally active surface. When first brought into use, care must be taken to allow copper-nickel alloys to form their protective corrosion resistant surface freely. Normally, this protective film will develop in six to eight weeks. Contact with other less noble metals or with cathodic protection systems must be avoided to ensure development of the corrosion resistant surface film and the non-fouling properties.
  • 23. Copper-nickel alloys do not suffer the stress-corrosion problems associated with some other materials. Table 8 Comparison or corrosion behaviour of CuNi10Fe and CuNi30Fe in seawater Environmental Type of Service experience conditions corrosion CuNi10Fe CuNi30Fe Clean seawater at Uniform, general 0.0025- 0.0025- velocities up to 1 m/s 0.025 mm/a 0.025 mm/a Clean seawater at Impingement attack Satisfactory Satisfactory velocities up to 3.5 m/s * Polluted seawater Accelerated general Less resistant Preferred but not and pitting immune Entrained sand in seawater Accelerated general Unsuitable, Use and erosion exceptin CuNi30Fe2Mn2 mild conditions Accumulated deposits on Local attack Generally good Tendency to pit surface Hot spots due to local Local attack by Good Good but some overheating denickelification failures in extreme conditions Corrosion plus stress Stress corrosion Very resistant Very resistant (Vapour side conditions) Feedwater heaters working Exfoliation attack Resistant Susceptible under cyclic conditions Non-condensable gases † Local attack and Highly Resistant Most resistant general thinning Hydrogen sulphide in General attack Less Resistant Less Resistant desalination plant * Local velocities caused by obstructions can be very high. † lf concentration of CO2 is extremely high, stainless steel may be better cholce. ‡ Attack will increase in concentration or temperature. Table 6 – Fouling resistance of various alloys in quiet seawater Arbitrary Rating Scale of Fouling Resistance 90-100 Best Copper90/10 copper-nickel alloy 70-90 Good Brass and bronze 50 Fair 70/30 copper-nickel alloy, aluminium bronzes, zinc 10 Very Slight Nickel-copper alloy 400
  • 24. 0 Least Carbon and low alloy steels, stainless steels, nickel-chromium-high molybdenum alloys Titanium Above 1 m/s (about 3 ft/sec or 1.8 knots) most fouling organisms have increasing difficulty in attaching themselves and clinging to the surface unless already securely attached. (INCO) 9.1.3 Sea Water Intakes Sea water is frequently required in large quantities for cooling purposes. One of the problems associated with sea water intakes in marine- or land-based installations is the occurrence of gross marine fouling of the entry. This may be of soft growth, barnacles or bivalves. Not only can this restrict the water flow but the marine fouling may be detached from time to time and cause blockages in heat exchangers or severe mechanical damage to pumps and valves. Injection of chemicals such as chlorine can be effective against marine fouling organisms. However, additions must be closely controlled to be effective and even so, may have a detrimental effect on the installation and the environment near the outflow. Storage of bulk chlorine can also be hazardous. Adequate control is possible during steady-state running conditions but this becomes difficult during downtime when flow ceases. An alternative is to make intakes and intake screens of 90/10 copper-nickel which is resistant to fouling. The intake pipes themselves may be of copper-nickel or large concrete piping may be internally lined either by casting the concrete round a formed pipe or by attaching sheet inside pipes by rivets or adhesive. Figure 9Comparison of zinc anode protected steel
  • 25. Figure 10Large diameter concrete intake pipe 10 Materials for Heat Exchanger Tubes 10.1 Introduction Heat exchangers take heat from one fluid and pass it to a second. The fire-tube array of a steam engine is a heat exchanger, taking heat from the hot combustion gases of the firebox and transmitting it to the water in the boiler. The network of finned tubes in an air conditioner is a heat exchanger, taking heat from the air of the room and dumping it into the working fluid of the conditioner. The radiator in a car performs a similar function. A key element in all heat exchangers is the tube wall or membrane which separates the two fluids. It is required to transmit heat and there is frequently a large pressure difference across it. What are the best materials for making heat exchangers? Or, more specifically, what are the best materials for a conduction-limited exchanger, with substantial pressure difference between the two fluids?
  • 26. Figure 1 Schematic of a heat exchanger 10.2 Design Requirements FUNCTION Heat Exchanger OBJECTIVE Maximise heat flow per unit area, or per unit weight CONSTRAINTS (a) Support pressure difference p (b) Withstand chloride ions (c) Operating temperature up to 150°C (d) Low Cost 10.2.1.1 Table 1 10.3 The Model First, a little background on heat flow. Heat transfer from one fluid, through a membrane to a second fluid, involves convective transfer from fluid 1 into the tube wall, conduction through the wall, and convection again to transfer it into fluid 2. The heat flux q into the tube wall by convection (in units of W/m2) is described by the heat transfer equation: (1)
  • 27. in which h1 is the heat transfer coefficient and T1 is the temperature drop across the surface from fluid 1 into the wall. Conduction is described by the conduction (or Fourier) equation (2) where  is the thermal conductivity of the wall (thickness t) and T12 is the temperature difference across it. It is helpful to think of the thermal resistance at surface 1 as 1/h1; that of surface 2 is 1/h2; and that of the wall itself is t/. Then continuity of heat flux requires that the total resistance 1/U is (3) where U is called the 'total heat transfer coefficient '. The heat flux from fluid 1 to fluid 2 is then given by (4) where T is the difference in temperature between the two working fluids. When one of the fluids is a gas, as in an air conditioner, heat transfer at the tube surface contributes most of the resistance; then fins are used to increase the surface area across which heat can be transferred. But when both working fluids are liquid, convective heat transfer is rapid and conduction through the wall dominates the thermal resistance. In this case simple tube elements are used, with their wall as thin as possible to maximise /t. We will consider the second case: conduction limited heat transfer. Then 1/h1 and 1/h2 are negligible when compared with t/, and the heat transfer equation becomes (5) Consider, now, a heat exchanger with many tubes, each of radius r and wall thickness t with a pressure difference p between the inside and outside. Our aim is to select a material to maximise the total heat flow, while safely carrying the pressure difference p. The total heat flow is (6) where A is the total surface area of tubing.
  • 28. This is the objective function. The constraint is that the wall thickness must be sufficient to support the pressure difference p. This requires that the stress in the wall remain below the elastic limit (yield strength) el (times a safety factor, which need not be included in this analysis): (7) Eliminating t between the last two equations gives (8) The heat flow per unit area of tube wall, Q/A, is maximised by maximising the performance index: (9) Four further considerations enter the selection. It is essential to choose a material that withstands corrosion in the working fluids, which we take here to be water containing chloride ions (sea water). Cost will naturally be of concern. The maximum service temperature must be adequate and the material should be available as drawn tube. 10.4 The Selection A preliminary selection using the Generic filter is shown in Figures 2-4. The first chart is of elastic limit versus thermal conductivity, to allow us to maximise the value of M1. The second stage shows maximum service temperature plotted as a bar-chart against resistance to sea-water, selecting materials with high temperature resistance and high resistance to corrosion in sea-water. The last stage shows a bar chart of material cost against available forms, selecting cheap materials that are available as sheet or tube.
  • 29. Figure 2 A Chart of Elastic Limit versus Thermal Conductivity Figure 3 A Bar-chart of Maximum Service Temperature versus Resistance to Sea-Water Corrosion
  • 30. Figure 4 Material Cost against Available Forms The results of this selection are shown in Results Table 1, and they suggest that it may be worth transferring the selection criteria to the coppers database to refine the search for a suitable material. 10.5 Results Material (ranked by M1) Comment Have the best performance index, but relatively poor corrosion High Conductivity Coppers resistance Brasses Again, relatively poor corrosion resistance Wrought Martensitic Stainless A good choice, but steel is more dense than copper Steel Aluminium Bronzes An economical and practical choice
  • 31. 10.5.1.1 Table 1 The Results of the Selection using the Generic Filter Material (ranked by M1) Comment 90/10 Aluminium bronze, cold wkd (wrought) The aluminium bronzes are cheap 92/8 Aluminium bronze, hard (wrought) 93/7 Aluminium bronze, hard (wrought) 95/5 Aluminium bronze, 1/2 hard (wrought) 95/5 Aluminium bronze, hard (wrought) Nickel iron aluminium bronze, as extruded The Nickel iron aluminium bronzes are more corrosion (wrought) resistant Nickel iron aluminium bronze, hot wkd (wrought) 10.5.1.2 Table 2 The Results of the Selection by expanding the coppers branch 10.6 PostScript Conduction may limit heat flow in theory, but unspeakable things go on inside heat exchangers. Sea water—often one of the working fluids—seethes with biofouling organisms which attach themselves to tube walls and thrive, creating a layer of high thermal resistance and impeding fluid flow, like barnacles on a boat. Some materials are more resistant to biofouling than others; copper-nickel alloys are particularly good, probably because the organisms dislike copper salts, even in very low concentrations. Otherwise the problem must be tackled by adding chemical inhibitors to the fluids, or by scraping—the traditional winter pass-time of boat owners. It is sometimes important to minimise the weight of heat exchangers. Repeating the calculation to seek materials for the lightest heat exchanger gives, instead of M, the index:
  • 32. (10) where  is the density of the materials from which the tubes are made. This is quite a different index—the strength varies to the power 2 because the weight depends on the wall thickness, and from Eqn 7 we know that wall thickness varies as 1/strength. Of course, all copper alloys have roughly the same density, so there is little point applying this index within the coppers in the database—but if copper alloys were compared with stainless steels at the Generic level, then it would be relevant. 11 Materials in Seawater Reverse Osmosis (SWRO) Plants6 In SWRO plants the operating environments are much less severe than in MSF plants. For example, the operating temperatures are much lower (below 50o C and non-condensable gases (e.g. CO2 , O2 , H2S NH3, Br2 etc) are not involved during seawater conversion. Austenitic stainless steels are the conventional materials used for high pressure piping leading to RO membrane module, brine rejection pipe, product water outlet pipe and high pressure pumps. In SWRO plants, high velocities of the feed water and design do not encourage crevice formation. However, high pressure pipings (close to weld or heat affected zone) headers, connectors, flanges, seals of pumps and membrane containment vessels are prone to crevice corrosion attack in case stagnant conditions are developed or deposits are formed in the piping system due to operational problems. The performance of materials in different SWRO plants is given in Table 4. 6 http://www.swcc.gov.sa/files/assets/Research/Technical%20Papers/Corrosion/RELEVANCE%20OF%20CORROSION %20RESEARCH%20IN%20THE%20MATERIALSELECTION%20FOR.pdf
  • 33.
  • 34. 11.1 Use of Superior Materials 11.1.1 Flash Chambers The use of stainless steel cladding or Cu/Ni cladding on mild steel in all the stages or in the first few stages and that of bare CS in the remaining stages appear to work very well in evaporators of the desalination plants. Keeping in view the existing materials, the evaporators are designed with a high corrosion allowance therefore, the chambers are not much affected by general or uniform corrosion. However, localized corrosion problems are quite frequent and troublesome and are the cause of concern During shut down, slow moving or stagnant high chloride brine, crevices (formed by salt and by scaling) and D.O. produce most favourable environment for initiating and propagating corrosion process. Use of high alloy stainless steels, Ni-base alloys or titanium as construction materials could perhaps be the ideal solution to avoid corrosion in flash chambers. Even considering these materials as the best proposition for long term trouble free operational life of the plant, the exorbitant cost would not permit their use as constructional material. Use of cement-concrete as construction material appears to be quite promising due to its low cost, strength and durability. Erosion-corrosion resistance of the cementitious material under conditions of high flow corrosive brine and thermal stresses and airtightness of the structures are the problems which are to be looked into. 11.1.2 Heat Exchangers The predominant cause of the failure of heat exchanger tubes is circulating water flow conditions resulting in tube inlet erosion/corrosion. This tube inlet damage is almost located in the first 150 mm of the tube inlets and often results in perforation. 11.1.3 Relevance of Corrosion Research in the Material Selection Cu-Ni (90/10 or 70/30), modified alloy Cu-Ni-Fe-Mn (66/30/2/2) or Ti are the materials used for heat exchanger tubes. The choice of the most suitable material depends upon the system (brine heater, heat recovery or heat rejection) to be considered. Titanium though costly has replaced Cu/Ni alloys for heat rejection and brine heater tubes due to its excellent erosion-corrosion resistance and heat transfer properties. Titanium has the tendency to undergo crevice corrosion specially at high temperatures. Addition of precious metals to titanium though make it slightly more expensive but increases its resistance to crevice corrosion tremendously. Alloys like Ti-0.15pd, Ti-005u-0.05Niand Ti-0.05pd-.3 Cu have excellent resistance towards crevice corrosion. Tables 5 and 6 provide some physical properties data relevant to heat transfer tubes including failure rates and cost. Conductive plastic composites containing high aspect ratio fillers (brasses, Al, Ni-plated mica, stainless steel fibres) have thermal conductivity many magnitude higher than the case polymer. These materials could be easier to fabricate, stronger, immune to corrosion and erosion,
  • 35. possessing good heat transfer properties and should be cheaper than the traditional7 heat exchanger materials.8 11.1.4 Venting System Conventional materials like CS cladded with SS 304, 316 or Cu-Ni which were previously employed in ejector body, nozzle and condenser, pipings showed pitting, SCC, metal loss or erosion, are now replaced by more superior materials like Incoloy 825, 254SM0 or FRP. 7 Saricimen, H., et al, “Performance of Austenitic StainlessSteels in MSF Desalination Plant Flash Chambers in the Arabian Gull” Desalination October, 1990. 8 Malik, A.U., and Kutty, Mayan, A., “Corrosion and Materials Selection in Desalination Plants” Proc. SWCC Operation and Maintenance Conference, April 27-29, 1992 p. 304.
  • 36. 11.1.5 Pumps Discharge columns and diffusers of brine recycle and blow down pumps which are usually made of Ni-resist showed SCC, fatigue or erosion due to porosity, lack of stress relieving operation and poor casting. Replacements with more expensive materials like SS316 or Duplex SS 2205 appear to overcome most of the erosioncorrosion problems.
  • 37. 11.1.6 Pipings Cement concrete (CC), reinforced cement concrete (RCC) and prestressed concrete (PC) which have been conventional material for product water transmission pipe lines showed frequent failures mainly due to rebar corrosion. The replacement of these materials with fusion bonded epoxy (FBE) or urethane (FBU) appears to minimize the risk of failure. Coating of rebars with FBE or FBU is though costlier but provide protection against corrosion. 12 Conclusion All in all, you can see that desalination plant has to adapt the nature of the environment. Environment won’t forgive the material of desalination plant. Therefore, you need to select the material that can adapt the environment and resist the corrosion. Corrosion is the main part of material selection. It attacks almost every part of desalination plant. It results from stagnancy, deposition, dealloying, galvanic couplation, dealloying and vapor space attack. The local attack (pitting, crevice) can be avoided in most of the cases by minimizing dissolved oxygen level of brine and incondensable gases, proper flushing and keeping an inert atmosphere during shut down, mechanical or chemical cleaning of deposits and maintaining C.P.