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You are on page 1/ 13

Best Practice

SABP-A-021 6 September 2008


Corrosion Control in Desalination Plants
Document Responsibility: Materials and Corrosion Control Standards Committee
Saudi Aramco DeskTop Standards
Table of Contents
1 Scope and Purpose................................................ 2
2 Conflicts and Deviations......................................... 2
3 References............................................................. 2
4 Definitions and Abbreviations................................. 2
5 Process Considerations......................................... 3
5.1 Introduction...................................................... 3
5.2 Process Descriptions....................................... 3
5.2.1 Multiple Stage Flash Evaporation......... 3
5.2.2 Multiple Effect Distillation...................... 4
5.2.3 Reverse Osmosis.................................. 4
5.3 Corrosive Species........................................... 5
6 Damage Types....................................................... 5
6.1 Damage Mechanisms...................................... 5
6.1.1 Pitting.................................................... 5
6.1.2 Crevice Corrosion................................. 5
6.1.3 Stress Corrosion Cracking.................... 6
6.1.4 Galvanic Corrosion............................... 6
6.1.5 Microbially Influenced Corrosion........... 6
6.1.6 Underdeposit Corrosion........................ 6
6.2 Damage Locations.......................................... 6
6.2.1 Multiple Stage Flash Evaporation......... 6
6.2.2 Multiple Effect Distillation...................... 7
6.2.3 Reverse Osmosis................................. 8
7 Corrosion Control Options...................................... 8
7.1 Dechlorination................................................. 8
7.2 Venting............................................................ 8
7.3 Materials Selection.......................................... 9
7.3.1 Metallic Materials.................................. 9
7.3.2 Non-Metallic Materials........................ 10
7.4 Chemical Inhibition........................................ 10
7.5 Cathodic Protection....................................... 11
8 Corrosion Monitoring............................................ 11
8.1 Inspection...................................................... 11
8.2 Stream Analysis............................................ 11

Previous Issue: New Next Planned Update: TBD


Page 1 of 13
For additional information, contact Isaias, Nicos Philippou on 966-3-8760249
Copyright©Saudi Aramco 2008. All rights reserved.
Document Responsibility: Materials and Corrosion Control SABP-A-021
Issue Date: 6 September 2008
Next Planned Update: TBD Corrosion Control in Desalination Plants

1 Scope and Purpose

This SABP provides guidelines that will improve the integrity of desalination plants
through a fundamental understanding of the damage mechanisms, process parameters,
inspection techniques, corrosion monitoring, analytical needs and corrosion control
options.

It is based on current industry experiences and recent integrity assessments of


desalination plants in Saudi Aramco by an inter-departmental and multidisciplinary
team of experts. It is meant for internal use only.

2 Conflicts and Deviations

If there is a conflict between this Best Practice and other standards and specifications,
please contact the Coordinator of ME&CCD/CSD.

3 References

3.1 Saudi Aramco References

Saudi Aramco Engineering Procedure


SAEP-1135 On-Stream Inspection Administration

Saudi Aramco Engineering Standards


SAES-L-132 Material Selection for Piping Systems
SAES-W-010 Welding Requirements for Pressure Vessels
SAES-W-011 Welding Requirements for On-Plot Piping

3.2 Industry Codes and Standards

American Petroleum Institute


API RP 570 Inspection, Repair, Alteration and Rerating of In-
Service Piping Systems

American Water Works Association


AWWA M46 Reverse Osmosis and Nanofiltration

4 Definitions and Abbreviations


ASME American Society of Mechanical Engineers
CO2 Carbon Dioxide

Page 2 of 13
Document Responsibility: Materials and Corrosion Control SABP-A-021
Issue Date: 6 September 2008
Next Planned Update: TBD Corrosion Control in Desalination Plants

MED Multiple Effect Distillation


mpy Mils per Year
MSFE Multiple Stage Flash Evaporator
ORP Oxidation Reduction Potential (REDOX Potential)
PFD Process Flow Diagram
PREN Pitting Resistance Number
RO Reverse Osmosis
SCC Stress Corrosion Cracking
SS Stainless Steel
TDS Total Dissolved Solids

5 Process Considerations

5.1 Introduction

The primary function of a desalination plant is to reduce the TDS content of


water, rendering it fit for potable or process applications. There are several
different desalination processes, but the three that are widely used within Saudi
Aramco plants are MED, MSFE and RO.

5.2 Process Descriptions

5.2.1 Multiple Stage Flash Evaporation

Figure 1 shows a schematic of a Single Effect Multiple Stage Flash


Evaporator. The process principle of flash evaporation is that the
maximum amount of energy that can be stored in water at its boiling
point decreases as the water pressure is reduced. Therefore, when hot
brine at its boiling point flows into a vessel operating at a lower pressure,
the excess energy forms steam by flashing the hot brine. This reduces
the temperature of the brine to its boiling point at the operating pressure.
A multistage flash evaporator utilizes this principle to produce distillate
and it has the following two main sections:
1) Heat Input

External energy is added to the recirculated brine to increase its


temperature to 121ºC (250ºF) by using live steam in a shell and tube
heat exchanger. Note that 121ºC is the highest allowable operating
temperature and usually multi stage flash evaporators are designed
to operate at 100ºC to reduce the scaling tendency of the water.

Page 3 of 13
Document Responsibility: Materials and Corrosion Control SABP-A-021
Issue Date: 6 September 2008
Next Planned Update: TBD Corrosion Control in Desalination Plants

2) Heat Removal

Internal heat is removed from the flashed steam in the last stage by
using raw seawater in the tube condenser to reduce the temperature
to 38ºC (100ºF). The overall operating temperature range of 121-
38ºC (250-100ºF) determines the efficiency of this process. The
greater the temperature difference, the more product water is
produced. These temperatures are limited by natural conditions.
The lower temperature is determined by the temperature of the raw
seawater. The higher temperature is set by the solubility of calcium
sulfate in the recirculated brine that is in contact with the heat
transfer surfaces in the brine heater.

5.2.2 Multiple Effect Distillation

Figure 2 shows a schematic drawing of a typical MED unit. In an MED,


water vapor is produced in the first effect (vessel) by spraying feedwater
onto a hot tube bundle. The heat source for the tube bundle is steam
from a low pressure boiler. In giving up its latent heat to the feedwater,
the steam condenses to give high purity distillate, which is collected and
is product water. The vapor produced in the first effect is passed to a
tube bundle in the second effect where its heat of condensation is used to
evaporate more water from the solution at a lower temperature and
pressure. This second quantity of water vapor then passes to a third
effect at lower temperature and pressure than the second and the process
is repeated, producing additional vapor. The optimum number of effects
is determined by the overall temperature difference available, the
temperature and pressure differences required per effect to maintain a
satisfactory production rate, and the additional costs of adding each
effect.

5.2.3 Reverse Osmosis

Reverse Osmosis (RO) is a membrane based desalination technique. The


principle of RO is that when two solutions of differing salt
concentrations are separated by a semi-permeable membrane, the natural
tendency is for water to flow from the dilute to the more concentrated
solution. The difference in head between the two solutions is the
osmotic pressure. On applying a pressure to overcome the osmotic
pressure, the flow direction is reversed, hence producing water with a
lower salt concentration. Industrially, RO membranes are usually
fabricated in a spiral wound configuration. The individual membrane
elements of around 1meter in length are then arranged in series in a long
pressure vessel (with typically 5-8 membranes per vessel).

Page 4 of 13
Document Responsibility: Materials and Corrosion Control SABP-A-021
Issue Date: 6 September 2008
Next Planned Update: TBD Corrosion Control in Desalination Plants

5.3 Corrosive Species

CO2 – carbon dioxide is formed in thermal desalination systems as a result of the


thermal decomposition of bicarbonates found in seawater.

Oxygen – reacts with carbon steel to give general corrosion. Reacts


synergistically with ammonia to increase corrosion of copper alloys.

Chlorides – experience has shown that > 500 ppb chloride levels can accelerate
the pitting corrosion of austenitic stainless steel.

Bromine – bromine is another of the halogens. Bromides are naturally present in


seawater and at the temperatures found in thermal desalination systems can
decompose to give gaseous bromine. Like chlorine bromine can cause
aggressive pitting in stainless steels.

6 Damage Types

6.1 Damage Mechanisms

6.1.1 Pitting

Pitting is a form of extremely localized corrosion that leads to the


formation of small holes (pits) in the metal. The presence of chlorides in
seawater significantly aggravates the conditions for formation and
growth of pits through an autocatalytic process. The pits become loaded
with cations through anodic dissociation. Chloride ions become
concentrated in the pits to maintain charge neutrality, encouraging the
reaction of positive metal ions with water to form hydroxide corrosion
products and hydrogen ions. The pits are now weakly acidic, which
accelerates the process. Bromides in seawater can also initiate pitting.
Stagnant water conditions favor pitting, which means that proper drain
down and lay-up procedures have to be followed in order to avoid
corrosion occurring during equipment downtime.

6.1.2 Crevice Corrosion

Crevice corrosion occurs in restricted regions, such as at a bolted joint.


Crevice corrosion is initiated by a depletion of the dissolved oxygen in
the restricted region. As the supply of oxygen within the crevice is
depleted, because of cathodic oxygen reduction, the metal surface within
the crevice becomes anodic, the anodic current is balanced by cathodic
oxygen reduction from the region adjacent to the crevice. The ensuing
reactions within the crevice are the same as those described for pitting
corrosion: halide ions migrate to the crevice, where they are then

Page 5 of 13
Document Responsibility: Materials and Corrosion Control SABP-A-021
Issue Date: 6 September 2008
Next Planned Update: TBD Corrosion Control in Desalination Plants

hydrolyzed to form metal hydroxides and hydrochloric acid.

6.1.3 Stress Corrosion Cracking (SCC)

Stress corrosion cracking can be defined as a failure mechanism by


which high aspect ratio flaws (cracks) are initiated and grow under the
combined effect of a tensile stress together with the chemical or electro-
chemical effects of the environment to which it is exposed. Austenitic
stainless steels are prone to SCC in the presence of chlorides, especially
at higher temperatures (>50°C). SCC is very unlikely in RO plants due
to lower temperatures, but can be encountered in the higher temperature
parts of thermal desalination equipment.

6.1.4 Galvanic Corrosion

When two or more different sorts of metal come into contact in the
presence of an electrolyte a galvanic couple is set up as different metals
have different electrode potentials This leads to the anodic metal
corroding more quickly than it otherwise would; while the corrosion of the
cathodic metal is retarded even to the point of stopping. The presence of
electrolyte and a conducting path between the metals may cause corrosion
where otherwise neither metal alone would have corroded.

6.1.5 Microbially Influenced Corrosion (MIC)

Microbially Influenced Corrosion is an underdeposit type corrosion


mechanism. The presence of bacteria and other microorganisms on the
surface of a material (a biofilm) can alter the kinetics of the corrosion
process. The metabolites of certain species of bacteria can reduce the pH
by up to three pH units. MIC normally produces corrosion pits, either as
a result of the pH depression, or due to underdeposit corrosion (see
section 6.1.6).

6.1.6 Underdeposit Corrosion

Underdeposit corrosion can occur under scale deposits, or under slime


mass. Both scale and slime masses produce a differential aeration cell.
The area under the deposit becomes anodic relative to the deposit free
surrounding area, causing severe localized attack.

6.2 Damage Locations

6.2.1 Multiple Stage Flash Evaporation

Typical corrosion mechanisms and the locations that these mechanisms


have been found in MSFE units are shown in Table 1. In general, the

Page 6 of 13
Document Responsibility: Materials and Corrosion Control SABP-A-021
Issue Date: 6 September 2008
Next Planned Update: TBD Corrosion Control in Desalination Plants

majority of the corrosion found in MSFE is concentrated in the higher


temperature sections.

Table 1 – Typical Corrosion Mechanisms and Locations

Location Material Corrosion Mechanisms


Seawater Strainers 316 SS Pitting
316 SS Pitting, MIC (heat rejection stages only), SCC
Flash Chambers
317 SS Pitting, MIC (heat rejection stages only), SCC
90/10 Cu/Ni Erosion
Ejector condensers 316 L Pitting
254 SMO Crevice Corrosion
90/10 Cu/Ni Pitting
316 SS Pitting, galvanic corrosion, SCC
Tube Sheets
904L SS Crevice Corrosion
254 SMO Crevice Corrosion
90/10 Cu/Ni Erosion, pitting
Heat Recovery Tubes 70/30 Cu/Ni Erosion, pitting
Titanium Hydriding
90/10 Cu/Ni Erosion, pitting, underdeposit corrosion
Heat Rejection tubes 70/30 Cu/Ni Erosion, pitting, underdeposit corrosion
Titanium Hydriding
316 SS Pitting, SCC
Evaporator box
317 SS Pitting, SCC

6.2.2 Multiple Effect Distillation

Table 2 shows the damage mechanisms and locations that the damage
has occurred for MEDs. This data was compiled from both operating
experience in Saudi Aramco plants and from a review of the published
literature.

Table 2 – Materials Employed in MED Plants and Associated Damage Mechanisms

Location Material Corrosion Mechanisms


Seawater Strainers 316 SS Pitting
90/10 Cu/Ni Erosion
Distillate Condenser Al-brass 76/22/2 Erosion
Aluminum Erosion
90/10 Cu/Ni Erosion
Vacuum Ejectors
316 SS Pitting
Thermocompressor 90/10 Cu/Ni Erosion
90/10 Cu/Ni Pitting
316 SS Pitting
Tube Sheet
904L SS Crevice Corrosion
254 SMO Crevice Corrosion

Page 7 of 13
Document Responsibility: Materials and Corrosion Control SABP-A-021
Issue Date: 6 September 2008
Next Planned Update: TBD Corrosion Control in Desalination Plants

Location Material Corrosion Mechanisms


90/10 Cu/Ni Erosion, pitting
70/30 Cu/Ni Erosion, pitting
Evaporator Tubes Aluminum Erosion, pitting
Titanium Hydriding
Al-5052 Erosion, pitting
316 SS Pitting
Evaporator box
317 SS Pitting
316 SS Pitting
Interconnecting Piping
317 SS Pitting

6.2.3 Reverse Osmosis

With RO plants, all metallic piping is subject to corrosion. Welds are


normally the most susceptible location within the piping systems, with
pitting corrosion at weldments being very common.

7 Corrosion Control Options

7.1 Dechlorination (MSFE/MED/RO)

Dechlorination is important to prevent pitting corrosion and/or stress corrosion


cracking in austenitic stainless steels. Most thermal plants use significant
amounts of austenitic materials for the construction of the main shell of the
evaporators, evaporator tube sheets and interstage ducting. Feedwater to most
thermal plants is chlorinated to prevent biofouling of the strainers and feedwater
canals. Dechlorination is performed by the addition of sodium bisulfite to the
feedwater. Sodium bisulfite reacts extremely rapidly with free chlorine,
producing sodium sulfate. It is important to inject the bisulfite sufficiently far
upstream of the basket strainers to ensure that no damage occurs to these units.
A good rule of thumb is that in turbulent flow conditions, six pipe diameters will
ensure good mixing. In the case of RO plants, the most common membrane
chemistry in Saudi Aramco is polyamide. Polyamide is chlorine sensitive, so
dechlorination is also essential to prevent damage to the membrane materials.

7.2 Venting (MSFE/MED)

In thermal desalination equipment, the vent system serves to create sufficient


vacuum for the water to evaporate. The vents also remove non-condensible
gases such as carbon dioxide and oxygen. Inadequate venting has resulted in
corrosion of copper alloy tubing in the hot stages of MSFEs. If vent problems
are suspected, then operations engineers need to work with the original
equipment manufacturers to resolve this issue. Enlarging vents without proper
attention to the vacuum conditions needed to maintain evaporation will lead to
reduced levels of water production.

Page 8 of 13
Document Responsibility: Materials and Corrosion Control SABP-A-021
Issue Date: 6 September 2008
Next Planned Update: TBD Corrosion Control in Desalination Plants

7.3 Materials Selection

7.3.1 Metallic Materials

The most common construction materials for thermal desalination plants


are stainless steels and copper alloys.

Stainless steels can give good performance, but great care has to be taken
with both the grade of stainless to be used and the surface preparation of
the steels (especially welds) if pitting corrosion or SCC is to be avoided.

One method of ranking stainless steels for pitting resistance is by the


Pitting Resistance Number (PREN). The PREN is an empirical means of
comparing stainless steels pitting resistance based on the composition of
the alloy. The most commonly used formula for calculating PREN is:

PREN = Cr + 3.3Mo + 16N

The PREN numbers for alloys often used in the fabrication of


desalination equipment are shown in Table 3. For use in seawater, a
material should have a PREN of >40.

Table 3 – PREN Numbers and Compositions for Stainless Steels

Grade Type Cr Mo N PREN


Austenitics
1.4301 304 17.0-19.5 NS 0.11max 17.0-20.8
1.4311 304LN 17.0-19.5 NS 0.12-0.22 18.9-23.0
1.4401 316 16.5-18.5 2.0-2.5 0.11max 23.1-28.5
1.4406 316LN 16.5-18.5 2.0-2.5 0.12-0.22 25.0-30.3
1.4539 904L 19.0-21.0 4.0-5.0 0.15max 32.2-39.9
1.4547 254SMO 19.5-20.5 6.0-7.0 0.18-0.25 42.2-47.6
Duplex
1.4362 SAF 2304 22.0-24.0 0.1-0.6 0.05-0.20 23.1-29.2
1.4462 SAF 2205 21.0-23.0 2.5-3.5 0.10-0.22 30.8-38.1
1.4410 SAF 2507 24.0-26.0 3.0-4.0 0.24-0.35 37.7-46.5
1.4501 Zeron 100 24.0-26.0 3.0-4.0 0.2-0.3 37.1-44.0

From this table it can be seen that the lower grade austenitics such as 304
are not suitable for seawater use. 316 Stainless stell has been used with
mixed success. As steel makers have improved control of their alloying
processing, in recent years the trend has been to control chromium
contents close to 2%. As the chromium content is lowered, so is the

Page 9 of 13
Document Responsibility: Materials and Corrosion Control SABP-A-021
Issue Date: 6 September 2008
Next Planned Update: TBD Corrosion Control in Desalination Plants

PREN and the material is more likely to corrode. In recent years Saudi
Aramco has specified 317SS as the minimum level austenitic stainless
steel for seawater applications, as this material contains more chromium
than 316 SS and is therefore more corrosion resistant.

Copper alloys have given satisfactory corrosion performance in


seawater, being almost immune to chloride corrosion. However, the
copper alloys are more prone to erosion than stainless steels. Pollution
of seawater with sulfides or compounds that can decompose to give
ammonia has also caused corrosion problems with copper alloys. The
copper alloys used in desalination applications are shown in Table 4.

Table 4 – Chart of Copper Alloys Used in Desalination Plants

NOMINAL COMPOSITION 5
ALLOY UNS Number
Cu Zn Al Ni Fe Mn As
Aluminium brass 76 22 2 - - - 0.04 C68700
90-10 Cu-Ni Rem - - 10 1.5 1.0 - C70600
70-30 Cu-Ni Rem - - 30 0.6 1.0 - C71500
66-30-2-2 Cu-Ni Rem - - 30 2.0 2.0 - C71640

A further point to be considered when considering the use of copper


alloys is the downstream use of the desalinated water. In particular,
boilers are sensitive to the presence of copper in the feedwater. For 625
psig boilers, (the most common pressure in use in Saudi Aramco) ASME
guidelines limit the copper content to 15 ppb. Unless the plant also has
ion-exchange demineralizers to remove copper, copper alloy tubing
should not be used in plants where the thermal desalination units are to
supply boiler feedwater.

7.3.2 Non-Metallic Materials

Non metallic materials do not find much application in thermal


desalination plants, because of the higher temperatures employed in this
type of equipment. For RO plants, non-metallics are an attractive option.
All low-pressure piping can be fabricated from FRP. While FRP piping
is more expensive to purchase and install, the life cycle costs are usually
lower than for stainless steels as FRP does not corrode.

7.4 Chemical Inhibition

Corrosion inhibitors are not employed in desalination plants as very few


corrosion inhibitors are suitable for potable water use. The only chemicals that

Page 10 of 13
Document Responsibility: Materials and Corrosion Control SABP-A-021
Issue Date: 6 September 2008
Next Planned Update: TBD Corrosion Control in Desalination Plants

are used in desalination plants are antiscalants, (for both RO and thermal plants)
antifoams (thermal) and sodium sulfite for residual free chlorine scavenging (for
both RO and thermal plants).

7.5 Cathodic Protection

Cathodic protection is not a common means of preventing corrosion in


desalination plants. However, there have been occasions when sacrificial
anodes have been used, usually to try to prevent pitting and crevice corrosion of
the tubesheets, most notably when titanium tubes have been rolled into duplex
stainless steel (904L) tubesheets. Aluminum sacrificial anodes have been
successfully used to mitigate crevice corrosion at the tube/tubesheet interface.
Iron anodes have been used in water boxes and in the water chambers of
distillate condensers to prevent galvanic corrosion at the tube/tubesheet
interface. Zinc anodes should not be used in equipment containing copper
alloys, as the zinc can interfere with protective film development.

8 Corrosion Monitoring

Conventional corrosion monitoring techniques such as weight loss coupons and probes
are seldom used in any desalination plants. As stated earlier in this document, most
desalination plants rely heavily on the use of corrosion resistant alloys as materials of
construction. Conventional monitoring methods are not suited to determining the
corrosion mechanisms, such as SCC and pitting, that are the most likely modes of
failure in a desalination plant.

8.1 Inspection

• Equipment

Visual inspection, random ultrasonic thickness (UT) and wet fluorescent


magnetic particle testing (WFMPT) are commonly used to check for
localized corrosion and environmental cracking.

• Piping

Various techniques such as random ultrasonic thickness (UT), UT shear


wave (UTSW) of welds and radiography (RT) are used to detect metal loss,
weld preferential corrosion and fine cracking.

8.2 Stream Analysis

Analysis of the feedwater for both thermal and RO plants is important when the
water has been chlorinated to control micro and macrofouling. Austenitic
stainless steels are prone to pitting and/or SCC in chlorinated water, while

Page 11 of 13
Document Responsibility: Materials and Corrosion Control SABP-A-021
Issue Date: 6 September 2008
Next Planned Update: TBD Corrosion Control in Desalination Plants

polyamide RO membranes are irreversibly damaged by contact with chlorine.


To prevent damage caused by chlorine, the feedwater is treated with sodium
sulfite. On-line chlorine monitors have been tried to provide continuous, real-
time data. However, on-line free chlorine meters have to be calibrated at
frequent intervals, and the reagents that are used in these meters have a short
shelf-life. For on-line monitoring experience has shown that ORP is a better
method of determining if free chlorine is present.

Stream analysis is very important for the correct operation of Reverse Osmosis
equipment. A fuller discussion of the parameters that should be monitored for
RO operations purposes is beyond the scope of this document. Readers wishing
to know more should read the document cited in the references section of this
document.

Process Flow Diagram TTD


Temperature Scale

Top Brine Temperature ΔT T1


Rise
Q1 ΔT

ΔT
T1-T0
Q0
T’0 ΔT

T0 Heat
Product Rejection
Water Stages Heat Recovery Stages
Brine
Heater

Cl2
Injection Recycle
Pump
Decarbonator Deaerator

Blowdown
Pump
Acid Feed

Seawater Pump Make-up Water Treatment

Figure 1 – Schematic of a Single Effect Multiple Stage Flash Evaporator

Page 12 of 13
Document Responsibility: Materials and Corrosion Control SABP-A-021
Issue Date: 6 September 2008
Next Planned Update: TBD Corrosion Control in Desalination Plants

Steam Steam
Thermo compressor Vapor from 4th
effect

Vacuum System
Vent

Distillate
1st effect condenser
2nd effect 3rd effect 4th effect

Seawater
feed

Tube Reject seawater


bundle

Brine
Brine

Distillate

Figure 2 – Schematic of a Multiple Effect Distillation Unit

Revision Summary
6 September 2008 New Saudi Aramco Best Practice.

Page 13 of 13

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