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The role of duplex stainless steels

in petrochemical heat exchanger


applications

CONTENTS
Introduction

Organic acids ..

Chlorinated hydrocarbons ..
Cooling water, seawater cooling

6
7

Selection criteria . 8
Localised corrosion
Organic acids
Reference deliveries ... 13

For more information see


S-120-ENG Duplex stainless steels fighting corrosion
worldwide
S-33-41-ENG Corrosion resistance of modern duplex
stainless steel in organic acid environments
S-52-86-ENG Duplex stainless steels for use in organic
acid
S-51-57-ENG SAF 2507 for seawater cooled heat exchangers
S-91-57-ENG Welding practice for the Sandvik duplex
stainless steels SAF 2304, SAF 2205 and
SAF 2507
S-91-59-ENG Guidelines for tube-to-tubesheet joining
during fabrication of heat exchangers in
super duplex stainless steel SAF 2507.

Sandvik Steel has a quality system approved by internationally


recognised organisations and holds ASME Quality System
Certificate as Material Organization. Approval, by accredited third
party, to ISO 9001 is also held, as well as TV approvals to ADW0/TRD 100, VdTV 1153 and KTA 1408, and other approvals.

Sandvik, Sandvik SAF 2304, Sandvik SAF 2205 and Sandvik SAF 2507
are trademarks owned by Sandvik AB
Recommendations are for guidance only, and the suitability of a material
for a specific application can be confirmed only when we know the actual
service conditions. Continuous development may necessitate changes in
technical data without notice.

INTRODUCTION
FROM WHALE OIL TO
ADHESIVES
The versatility of chemicals derived
from organic oils was first discovered
through the exploitation of whale oil in
the nineteenth century. Domestic lighting was first made possible through the
use of this medium and was also the
basis for the establishment and growth
of some of the worlds major chemical
corporations. Thankfully the discovery
of another form of hydrocarbon in the
shape of crude oil provided an alternative source of domestic energy as well
as an abundant feedstock for the manufacture of the majority of todays consumable products. Fig. 1 summarises
the derivatives of natural gas and crude
oil and the finished products that are
manufactured from them.
In todays petrochemical market the
most important hydrocarbon raw materials following petroleum refining and
natural gas processing are ethylene,
propylene, butadiene, benzene, mixed
xylenes and methanol. Demand for
these products is expected to increase in
proportion to world demand for consumer products.
RELIABLE HEAT TRANSFER
Heat transfer is one of the fundamental
elements of hydrocarbon processing,

together with catalysis, thermal cracking, fluid flow and mass transfer.
Despite technological advances in the
area of compact heat exchangers, shell
and tube and air cooler type exchangers
are the most popular pieces of equipment in bulk petrochemical operations
thanks to their ability to accommodate
large heat loads and their ease of maintenance and cleaning. This popularity
will continue long into the future.
Reducing corrosion of materials and
reducing fouling of heat transfer surfaces is a high priority in the hydrocarbon processing industry. Corrosion and
fouling can in many cases reduce onstream time, increase maintenance and
therefore lower operating efficiency. In
these times of strong competition within the industry and in the spirit of increased efficiency, in line with stiffening environmental legislation, retrofitting operations in petrochemical
plants often involve the addition of new
or improved heat transfer equipment.
Such investment can be difficult to justify if the new equipment is still subject
to corrosion and fouling. There is therefore a demand for cost effective solutions to the potential problems that can
be encountered in heat transfer equipment. This demand can be satisfied in
many cases by the specification and

VINYL CHLORIDE

ADHESIVES

BUTADIENE
DETERGENT AND SOAPS
ETHYLENE DICHLORIDE

NATURAL GAS

PETROLEUM

ETHYLENE

ETHYLENE GLYCOL

PROPYLENE

ETHYLENE OXIDE

BUTYLENE

METHACRYLATE

BUTADIENE

MALAIC ANHYDRIDE

BENZENE

PTHALIC ANHYDRIDE

TOLUENE

ACRYLONITRILE

p-XYLENE

STYRENE

o-XYLENE

PHENOL

m-XYLENE

FORMALDEHYDE

NAPHTALENES

UREA

AMMONIA

MELAMINE

METHANOL

TOLUENE DIAOCYANATE

EXPLOSIVES
FERTILIZERS
FILMS AND FIBRES
PAINTS AND COATINGS
PESTICIDES AND HERBICIDES
PHARMACEUTICALS
POLYMERISING
POLYMERS/RESINS
RUBBERS AND ELASTOMERS

CARBON BLACK
OTHER ORGANIC CHEMICALS

SOLVENTS AND CLEANING COMPOUNDS

Fig 1.

installation of Duplex Stainless Steels


in critical applications. Petrochemical
and chemical applications account for
approximately a quarter of the total
spending on heat exchange equipment
world-wide. Almost two thirds of that is
reportedly spent on shell and tube
exchangers and air coolers. By virtue of
their application at elevated temperatures, heat exchangers can represent
something of a flashpoint when it concerns corrosion damage. It has become
common practice these days to retube
existing carbon steel tubular heat
exchangers with corrosion resistant
materials in the event of premature failure. This helps to increase plant lifetimes and reduce maintenance costs. A
greater awareness of the corrosive nature of todays petrochemical applications and the need to operate plant in a
highly efficient manner have also led to
the specification of new equipment in
more advanced materials.
MATERIALS IMPROVE
PROCESSES
In addition to solving ongoing maintenance problems, the integration of
materials engineering into chemical
processing technology can also help to
increase the operating window of specific pieces of equipment. Organic acid,
methanol and urea production are just
three current examples of where the
materials of fabrication constitute an
integral part of the process technology.
This brochure describes the application of one group of stainless steels, the
Duplex Stainless Steels, which was initially developed to combat common
problems associated with chloride bearing cooling waters and process fluids.
Thanks to their alloying and microstructure they can also offer a remarkable resistance to corrosive process environments, notably in the production of

organic acids, where equal or better


resistance to general corrosion than
high cost nickel base alloys has been
demonstrated.
Standard 300 series austenitic stainless steels have found wide application
in the petrochemicals industry particularly for use in piping systems and
instrumentation applications. Their
limited use in heat exchanger applications is due to susceptibility to stress
corrosion cracking (SCC) in chloride
bearing media at temperatures greater
than 50C. Duplex stainless steels have
a far greater resistance to SCC thanks to
their two phase, ferritic and austenitic
microstructure. Sandviks present
Duplex range includes a family of
alloys, namely SAF 2304, SAF 2205
and SAF 2507, that can be used to tackle corrosion in a broad range of environments. The super-duplex SAF 2507
can even be used in seawater cooling
applications. Not surprising since it
was this job that the material was
designed for. Due to the efficient use of
critical alloying elements such as chromium, molybdenum and most notably;
nitrogen these materials offer a cost effective alternative to carbon steels, copper base alloys, brasses and bronzes.
Duplex alloys can bridge the cost gap
between these traditional materials and
the expensive, nickel based and titanium alternatives while still giving the
performance level of the latter.
One of the great attractions of the
duplex family of alloys is its compatibility with the other groups of alloys
with respect to fabrication. Physical
properties such as the coefficient of
thermal expansion makes retubing of
carbon steel exchangers possible with
minimum modification. Also expansion only joining into lower strength
tubesheet materials such as CuNi and
Al-bronze is possible.

The major corrosion problems in petrochemical


heat exchangers
Organic Acids Formic acid, acetic acid, terephthalic acid
Organic Chlorides EDC, VCM, PVC and other chlorinated hydrocarbons
Utilities - Cooling Water including Seawater Cooling
Product Purity - Contamination by carbon steels and other
non passive materials
4

ORGANIC ACIDS
PROCESS
The reactive acid group (-COOH) is responsible both
for the wide use of these chemicals as well as their
resultant corrosive nature. They are slightly reducing in
nature and are often mixed with halides used as catalysts during their synthesis. The most corrosive of the
organic acids is formic, and the most widely used is acetic. Formic acid is also a common contaminant in acetic
acid processing.
Pure Terephthalic Acid (PTA) is an important feedstock in the manufacture of synthetic resins for plastics
manufacture. Acetic acid is one catalyst used in the oxidation of paraxylene which is the most common method
of manufacturing PTA.

Air Cooler
(Condenser)

Acetic
Acid
Raw
Material

Water
Steam

Reactor
Air
Distillation

Fig 2. Acetic acid plant.

COMMON MATERIALS OF CONSTRUCTION


General applications
AISI 304L
AISI 316L
AISI 317L
Demanding Environments
Nickel Alloys 600, 625
Hastelloy C-276
Titanium
Zirconium

PRACTICAL EXPERIENCE
In plant testing in a terephthalic acid plant
High alloy austenitics such as 2RK65 (904L) has been
successful in organic acid applications, but there is a
lack of references thus far for duplex stainless steels.
Through laboratory testing it is possible to rank different materials in terms of their corrosion resistance in
different organic acid containing solutions. However; It
is not practically possible to simulate real process environments. The only real way to compare materials performance in process is through in plant testing. The
table shows the respective corrosion rates of some stainless materials seen in coupon testing in a European PTA
plant using a process based on the oxidation of paraxylene in the presence of an acetic acid catalyst. People
familiar with this process will most likely recognise the
specific location of the coupons.
The table shows that corrosion from this process
environment results in unacceptably high corrosion

SANDVIK SUGGESTS
Duplex stainless steels show a remarkable resistance to
general corrosion by organic acids, even outperforming
some of the nickel based alloys in many cases.
However; the cost of these materials is close to their
austenitic cousins. Results from both laboratory research and in plant testing described below prove the
value of Duplex stainless steels as the most cost effective problem solver for organic acids production.

rates in the austenitic stainless steel AISI 317L whereas


SAF 2205 and SAF 2507 have very low rates.

Materials

AISI 317L
AISI 317L,
welded
SAF 2205
SAF 2205,
welded
SAF 2507
SAF 2507,
welded

Solution :
75% acetic acid,
25% H2O
Traces of Br, Co, Mn
Corrosion rate mm/y,
T=175C

Solution :
96% acetic acid,
3% H2O
Traces of Br, Co, Mn
Corrosion rate mm/y,
T=150C

0.44

0.67

0.47
0.012

0.68
0.06

0.027
0.004

0.072
0.011

0.006

0.016

CHLORINATED HYDROCARBONS
PROCESS
In the pure form organic chlorides are not corrosive but
when they condense in heat exchangers, a certain
amount of water is often present as a separate phase.
The resultant hydrolysis when the two media mix
results in the formation of hydrochloric acid.
Hydrochloric acid is one of the most corrosive mineral
acids and even at trace quantities in solution can cause
rapid attack of even corrosion resistant alloys.
Two of the most common processes for the chlorination of hydrocarbons are direct chlorination using Cl2 or
oxychlorination using HCl. Both processes rely heavily
on catalyst technology. Fig. 3 shows a simplified diagram describing oxychlorination used in the production
of ethylene dichloride (EDC), the most important feedstock in the manufacture of PVC.

EDC
Pre-condenser
EDC for final
processing to
Vinyl Chloride
Reactor

Quench Tower

Ethylene
Air
Hydrochloric Acid

Fig 3. EDC plant.

COMMON MATERIALS OF CONSTRUCTION


Carbon steel is used extensively in these plants, both for
columns and heat exchangers as well as piping systems.
Carbon steel could be considered satisfactory provided
the moisture content in the process can be kept under
close control. In practice this can be quite difficult to
achieve. Shut down periods can be particularly troublesome when equipment temperatures drop below the dew
point temperature of HCl.

SANDVIK SUGGESTS
The presence of aqueous HCl constitutes the major corrosion problem that can be experienced in these plants.
General corrosion of carbon steels, high risk of pitting
and stress corrosion cracking in standard AISI 300 series stainless steels and pitting of nickel based alloys are
the most likely failure modes. Nickel base alloys can be
useful when the corrosion mode is rapid and heavy
general attack, however if the risk is for localised corrosion then very often high performance duplex stainless
steels have an advantage due to higher alloying with
chrome, molybdenum and nitrogen. Nickel itself has
little effect on resistance to pitting attack.

PRACTICAL EXPERIENCE
Alkyl Chlorides
The resistance of the duplex stainless steels in HCl varies according to the composition of the material and the
characteristics of the acid. In a German petrochemical
plant a heat exchanger used to condense branched alkyl
chlorides at 75C was tubed with 22Cr duplex. The
alkyl chlorides themselves were not corrosive, however
the organic phase contained a certain amount of water
which condensed as a separate phase. The aqueous

phase absorbed some chlorides producing hydrochloric


acid. As a result the tubes corroded in a few months. The
form of corrosion was preferential attack of either one
of the phases which is normal under conditions of general corrosion. The outlet pipe of the exchanger which
was fabricated from the same material also corroded by
the same mechanism. In order to gain experience with
another material, the outlet pipe was replaced with SAF
2507. This has now been in operation for three years
without sign of corrosion.

COOLING WATER, SEAWATER COOLING


PROCESS
Cooling waters can vary in salt content from virtually
nil in de-ionised and fresh water up to 1.8% in seawater.
Water sources may also be polluted with sulphides,
ammonia and carbon dioxide amongst others as well as
carrying entrained solids. All these factors adjust the
corrosivity of the water dictating that careful consideration must be given to which materials may be used in
each case.
By far the most challenging test for materials in cooling water applications is in the case of seawater coolers.
Seawater cooled heat exchangers are subject to constant maintenance due to various problems caused by
this particular cooling medium.

FACTORS AFFECTING CORROSION


PERMORMANCE OF MATERIALS FOR
SEAWATER EXCHANGERS
High chloride content
Deposits and biofouling
Chemical treatments such as chlorination
Erosion due to entrained solids
Pollution by sulphides and ammonia

COMMON MATERIALS OF CONSTRUCTION


Suitable materials for construction of water cooled heat
exchange equipment must therefore have the correct
combination of properties to cope with the severity of
the water while at the same time being compatible with
process side conditions which may themselves be corrosive.
Traditional materials for cooling water service :
Carbon steel
AISI 304L/316L
CuNi, 70/30, 90/10
Admiralty brass
Main limitations
General corrosion of carbon steel
SCC of 300 series stainless steels
Erosion resistance of brass and CuNi
General corrosion of CuNi in the presence of
sulphides polluted waters

SANDVIK SUGGESTS
SAF 2304, SAF 2205 in chloride containing cooling
water (non seawater applications)
Excellent resistance to SCC
Excellent resistance to pitting up to specific limits

PRACTICAL EXPERIENCE
Retubing seawater coolers with SAF 2507
There are few materials solutions to seawater corrosion
problems available at reasonable cost. The kinds of
materials that can resist corrosion in seawater are
expensive and require special consideration when it
comes to manufacturing of equipment.
At a hydrocarbon processing plant in Singapore, land
reclamation led to increased amounts of sand in the seawater used for process cooling. At flowrates as low as
1 m/s heat exchangers tubed with admiralty brass started leaking prematurely.

The two candidate materials for retubing the exchangers were Titanium and SAF 2507.
Titanium tubes have been known to split during
heavy expansion during retubing operations. In addition, it is necessary to apply cathodic protection in header boxes to prevent galvanic corrosion of the brass
tubesheet. Under such circumstances brittle titanium
hydrides can form in the tubing greatly reducing the
integrity of the equipment.
As a result SAF 2507 was the selected material and
has been in service since 1993.

SAF 2507 for seawater cooling


Excellent resistance to SCC
Excellent resistance to pitting corrosion on chlorinated seawater
Excellent resistance to erosion corrosion
Excellent resistance to a wide range of process media.
All Sandvik's Duplex grades have excellent weldability
and fabricability enabling tube to tubesheet joining by
welding, expanding or a combination of both.

SELECTION CRITERIA
FOR DUPLEX STAINLESS STEELS IN HEAT EXCHANGERS
CONSIDERATIONS
Duplex stainless steels may be used in
many corrosive environments within
the temperature range of approximately
-50 to 300C.
When considering which duplex
stainless steel to use in a particular heat
exchanger application, the main concern is resistance of the material to
localised pitting corrosion.
The parameters affecting the pitting
tendency of a given stainless steel can
be defined as :
temperature
chloride content
oxidant content
pH
sulphide content
inhibiting ion content
flow rate
Brief consideration of these parameters
enables further simplification for grade
selection;
Oxygen is the most common oxidant
found in natural waters. Its content varies between 0 - 9 ppm between boiling
and 20C. The corrosivity of the waters
drops considerably when the oxygen
content drops clearly below 1 ppm.
Chlorine is another oxidant which is
commonly added to seawater exchangers to mitigate against biofouling.
Its effect is to considerably increase the
electrochemical potential and thus
increase the severity of the environment. Only materials with an exceptionally high resistance to pitting
should be used in systems containing
chlorinated seawater.
The pitting resistance is impaired by
stagnant solutions. High flowrates of
chloride containing water in tubular
heat exchangers will keep the surfaces
clean both from deleterious species at
pitting sites and from fouling which
could otherwise reduce heat transfer.
The following 4 factors are the most
critical in assessing the probability of
pitting attack :
1. high electrochemical potential
2. high chloride content
3. low pH
4. high temperature
8

Tube Wall

Temp
(C)
T(h)

Hot Fluid

Cold Fluid

MTT

T(c)

r(o)

r(f,o)

r(w)

r(f,i)

r(i)

1/U

Fig 4. Temperature drop through a tube wall from a hot to cold medium.

To predict whether pitting corrosion


will occur within a given set of environmental parameters it is necessary to
relate the Critical Pitting Temperature
(CPT) of the material in that environment to the Maximum Tube wall
Temperature (MTT) that will be experienced in the exchanger. The MTT can
be calculated using the following relation :
(1)

1
1
1
1
1
1
= + + + +
U h(o) h(w) h(f,o) h(f,i) h(i)

(2)

1
= r(o) + r(f,o) + r(w) + r(f,i) + r(i) = R
U

(3)

r(o)+r(f,o)
MTT = T(h) T(h) T(c)
R

Where :
U = overall heat transfer coefficient
h
= individual heat transfer coefficient
R = overall heat resistance (1/U)
r
= individual heat resistance (1/h)
o/i = outside/inside of tube
f
= fouling
w = tube wall
T(h) = temperature of hot fluid
T(c) = temperature of cold fluid
MTT= Maximum Tube wall Temperature

Thus, if the MTT is maintained


below the CPT of the material in a
given set of conditions then the risk of
localised corrosion may be disregarded. Should some of the required information not be available, a reliable, but
conservative, estimation can also be
made simply by using the temperature
of the warmest corrosive fluids on the
shell or tube side.
Many years of experience have enabled Sandvik to formulate a method of
laboratory testing for pitting resistance
that has correlated well to working
conditions when compared with practical experiences.
CRITICAL PITTING
TEMPERATURE CURVES
A rapid method of testing for the critical temperatures at which localised pitting corrosion takes place has been
developed by Sandvik and utilises a
potentiostat that simulates the oxidising nature of chloride containing process fluids and cooling waters. The
applied potential maintains the constant oxidising power of the solution in
which the materials are tested. With a
constant potential applied, the temperature of the solution is increased by
5C increments until localised corrosion is determined. This is defined as
the temperature at which the current
density measured on the surface of the
sample rises above a value of 10 A/cm2.
The method has been substantiated by
comparing the results of the testing
with data collected from real heat
exchanger applications.
The following step by step method
should be used :
1. Define chloride content and MTT.
2. Define pH, presence of oxidising
species and species that may act as
inhibitors.
3. Estimate oxidising character of the
solution preferably by measuring
the corrosion potential.
4. Check the diagrams and judge the
applicability of the steels under
consideration. Remember results
from testing are likely to be conservative.

Stress corrosion cracking


Temperature,C

Temperature,C

90

300

SCC

904L

SAF 2507
No cracking

N08028/Sanicro 28

SAF 2507
250

80

SAF 2205
150

70

SAF 2304

25 Cr Duplex

60

100

SAF 2205

50

AISI 304/304L

50

AISI 316/316L

Cl,%
12
15
20
25
NaCl, weight-%

40
3
5

6
10

9
15

Fig 5. Critical pitting temperatures (CPT)


for SAF 2507 and SAF 2205 in various concentrations of sodium chloride at +600 mV
vs SCE, neutral pH.

No SCC
0
0.0001

0.001

0.01

0.1

1
10
Cl, weight-%

Fig 8. SCC resistance for SAF 2507, SAF


2205 and SAF 2304 inoxygen-bearing neutral solutions.

General corrosion
Temperature C

Temperature, C
Boiling point curve

120

90

SAF 2507
6Mo + N
100

80

SAF 2507
80

70

60

25 Cr Duplex

60

SAF 2205

AISI
40 316L

50

20

40
5

AISI
316L
904L

SAF 2507

SAF
2205

SAF
2304
0

20

40

60

pH

Fig 6. Critical pitting temperatures (CPT)


for SAF 2507 and SAF 2205 in 3% NaCl
solutions with varying pH at +600 mV SCE.
CPT, 300 mV SCE, C

SAF
2304

80
100
H2SO4, weight-%

Fig 9. Isocorrosion diagram for SAF 2507,


SAF 2205 and SAF 2304 in sulphuric acid
(0.1 mm/year).

Temperature, C

Pitting
Boiling point curve

100

80
SAF 2205
60

SAF 2507
80

AISI 316L

SAF 2304

40

60
AISI
316L

AISI 304L
20

904L

40

No pitting
0
0.01 0.02

0.05 0.10 0.20

0.50 1.0 2.0


Cl, weight-%

Fig 7. Critical pitting temperatures (CPT)


for SAF 2205 and SAF 2304 in various concentrations of sodium chloride at+300 mV vs
SCE, neutral pH.

20
0

6Mo+N

SAF 2205
1

4
5
HCl, weight-%

Fig 10. Isocorrosion diagram for SAF 2507


and SAF 2205 in hydrochloric acid (0.1
mm/year).

PRACTICAL ASPECTS TO
SELECTING MATERIALS
While it has proved effective to select
materials for heat exchanger applications based on arbitrary laboratory test
results, it is also necessary to consider
certain aspects of operating heat exchangers that cannot be suitably represented in the laboratory testing.
Deposits
The most important consideration is
perhaps the potential for the build up of
deposits in or on the tubes. Such deposits may emanate from the process side,
for example from tenacious hydrocarbons and process slurries. Cooling
water sources may contain sand or
sediment that can lie in horizontally
mounted exchangers when operated at
low flowrates. Due consideration must
be given to the possibility of crevices
forming under these deposits which
may lead to corrosion taking place at
temperatures lower than the CPT of the
selected material.
Probably; two of the most potent
tools in selecting material for the
upgrading of heat exchangers are :
Previous experience with other
materials.
What has been the mode of failure
of the previously installed unit and
where have the problems occurred?
This information can be gathered
during inspection.
What material solutions have been
used successfully elsewhere?
Much information is available from
Sandvik reference lists, which present
data from plants worldwide where
duplex alloys have a proven track
record over a period of time.
These two items of information,
used in combination with the exchanger operating parameters, technical data
sheets and corrosion tables will enable
effective materials specification to be
made.

10

CORROSION IN ORGANIC ACIDS


Organic acids are widely used in the
chemical industry of today. One important reason is the reactive carboxylic
group (-COOH) in organic acids, which
forms a base for manufacturing of
various chemical compounds, ranging
from drugs to plastics and fibres.
The most common organic acids are:
Formic acid
HCOOH
Acetic acid
CH3COOH
Propionic acid CH3CH2COOH
Butyric acid
CH3CH2CH2COOH
Fatty acids, comprising six or more
carbon atoms are also relatively common, examples of these are stearic acid
and tall oil fatty acids. Another common acid is terephthalic acid, which is
used as an intermediate in polyester
fibre processing.
CORROSIVITY
Organic acids are usually slightly
reducing and they can, especially if
impurities are present in the process
solution, be relatively corrosive. As a
rule, the corrosivity of organic acids
increases as the size of the acid molecule decreases, which means that formic acid is the most aggressive of all
pure organic acids. Acetic acid is less
corrosive in its pure form, but in presence of impurities the corrosiveness
may increase substantially. Acetic acid
Temperature, C

0.8
0.6
0.4
0.2
0
C-276 C-22

C-4

SAF A 625
2507

SAF
2205

Fig 12. Corrosion rates of various alloys in


boiling 40% formic acid + 2000 ppm Cl. Test
time 1+3+3 days.

is also present as a solvent in the manufacturing of terephthalic acid, where


severe corrosive conditions may occur.
Propionic acid and butyric acid are less
aggressive but at high temperatures or
with presence of impurities they may
give corrosion problems on low alloyed
stainless steels. Fatty acids are less
aggressive, but the acids may be corrosive during processing, if lower molecular weight acids are remaining in
fatty acid mixtures, or if the fatty acid is
anhydrous.
Impurities are present in organic
acids as catalysts or contaminants such
as chlorides, ferric or cupric ions and
also as air or peroxide. Other examples

Temperature, C

B o i li n

100

Corrosion rate, mm/year


1.0

rve
p o int c u

SAF 2507
120

SAF 2304

904L

316L
SAF 2507
100

80
316L

80

304L

60
60
304L
40

40

20
0

20

40

60

80
100
HCOOH, weight-%

Fig 11. Isocorrosion diagram for SAF 2507


and SAF 2304 in formic acid.

20
0

20

40

60
80
100
CH3COOH, weight-%

Fig 13. Isocorrosion diagram 0.1 mm/year, in


acetic acid. Shaded area represents risk of
localized attacks on 304L steel. The curve for
the higher alloyed steels coincides with the
boiling point curve.

11

Corrosion rate, mm/year


0.05
>0.1
mm/
year

0
SAF
2205

SAF
2507

A 625

C4

C22

C276

Fig 14. Corrosion rates of various alloys in


acetic acid with anhydride and 200 ppm
chlorides.

Corrosion rate, mm/year


50% acetic acid
0.20
AISI 317L
AISI 316L
0.15

SAF 2205

0.10

N08028
Sanicro 28

SAF2507
No attack

0.05
6Mo+N
0
0

10

15

20
25
30
HCOOH, weight-%

Fig 15. Corrosion rates of SAF 2507 and


SAF 2205 in boiling mixtures of 50% acetic
acid and varying proportions of formic acid.
Test time 1+3+3+ days.

are formic acid or acetic anhydride


which may be present in acetic acid
processing. If cupric or ferric ions are
present, the conditions become more
oxidising, and the corrosiveness may
in fact decrease under certain conditions. On the other hand, simultaneous
presence of chlorides may give a risk
of pitting or stress corrosion cracking.
This implies that it may be difficult to
judge the performance of a certain
material if the process contains impurities, and as a rule organic acids are
almost never handled in their completely pure state.

12

MATERIALS OF CONSTRUCTION
Since organic acids are reducing, the
materials of construction should either
have high contents of Ni and Mo, or
they should be easily passivated. The
former group is characteristic for
Nickel base alloys, whereas the latter
is a typical feature of a duplex stainless
steel.
Standard austenitic stainless steels
may be used in organic acids at low to
moderate temperatures and concentration ranges. In more corrosive conditions, upgrading has to be done to
higher alloyed stainless steels, such as
the duplex stainless steels, or nickel
base alloys. Other materials such as
copper and aluminium may be used
but they are very sensitive to specific
process conditions. For instance, copper is attacked in presence of aeration
or cupric ions, whereas under deaerated conditions the resistance may be
very good, even above the atmospheric
boiling point.
FORMIC ACID
Formic acid is the most aggressive of
the organic acids. At temperatures up
to 40C Sandvik 3R12 may be used,
whereas at higher temperatures 3R60
may be used if the concentration is
low. At concentration exceeding 10%
and temperatures above 80C special
stainless steels must be used to keep
the corrosion rate low. The duplex
stainless steels Sandvik SAF 2304,
SAF 2205 and SAF 2507 have good
resistance within certain limits, at temperatures above 100C SAF 2507 is
the preferred material, except in boiling solutions in the concentration
range 40-90%, where the temperature
must be limited to approximately
100C. In boiling 40-90% formic acid
materials such as Hastelloy C-4 or
alloy 625 may be used.
The presence of impurities in formic
acid may increase corrosiveness substantially, this is especially true for ferric chloride and copper chloride, where
corrosion rate increases substantially.

In presence of chlorides but no oxidising agents such as the ferric or cupric


ions, SAF 2507 shows a performance
similar to or slightly better than alloy
625.
An isocorrosion diagram for various
alloys in formic acid is shown in figure11. Figure 12 shows corrosion rates
of various alloys in 40% formic acid
with an addition of chlorides.
ACETIC ACID
Acetic acid in its pure form is less
aggressive than formic acid. If no
impurities exist Sandvik 3R60 can be
used up to the boiling point at all concentrations, with the exception of concentrated anhydrous acetic acid, where
the solution will be more aggressive.
In anhydrous acetic acid and in acid
containing impurities such as chlorides, formic acid or acetic anhydride,
higher alloyed materials such as SAF
2507 or Hastelloy C-4 are preferred
materials of construction. Figure 13
shows the isocorrosion diagram in acetic acid. Figure 14 shows the corrosion
rate of various alloys in concentrated
acetic acid with an addition of acetic
anhydride and chlorides.
TEREPHTHALLIC ACID
When terephthalic acid is manufactured, the intermediate stages contain
catalysts such as MnAc and NaBr and
acetic acid is used as solvent (oxidation of paraxylene). In some cases
chloride contaminants may be present.
Terephthalic acid is very aggressive
and there is a risk of corrosion on
standard stainless steels. A high resistance to general corrosion and stress
corrosion cracking are criteria that
have to be fulfilled for materials of
construction. Both 3R12 and 3R60
have limited resistance in the process,
and therefore special grades such as
the duplex SAF 2205 and SAF 2507
are recommended.
In the plant testing in a terephthalic
acid plants has been performed on
SAF 2205 and SAF 2507, showing
very low corrosion rates, see page 5.

REFERENCE DELIVERIES
ORGANIC ACIDS
Application
Country
Size
Service conditions

Previous experience
Sandvik SAF 2205

Application
Country
Size and quantity
Service conditions

Chloride salts
Italy
38.1 x 1.65 mm
Tube side
Glutamic acid
1620% Cl, 1.83% SO4 (2),
Mg, Na, K, Ca, pH 45
Temperature max 85C (185F)
Shell side
Steam at max 115C (239F)
316L tubes failed due to SCC.
Tubes in service since 1983 with excellent performance.

Sandvik SAF 2205

Caprolactam
Italy
19.05 x 1.65 mm, 11 600 m (38000 ft)
Tube side
Diathermic oil
Inlet 325C (617F)
Pressure 15.3 bar (222 psi)
Shell side
Benzoic acid + underproducts
Inlet 285C (545F)
TP316L and 317 failed due to corrosion and fretting at baffle
plates. Severe fouling on shell side.
Two reboilers installed in early 1984.

Application

Reboiler/Condenser

Country

USA

Size

25.4 x 1.65 mm, test tubes

Service conditions

Tube side
Shell side

Previous experience

Previous experience

Methanol vaporising at 120C (248F)


Overhead gases condensed to 20-25% acetic acid
T = 120-130C (248-266F)
AISI 316L, AISI 317L and Hastelloy C276 corroded.

Sandvik SAF 2507

Installed in 1991. In service inspection 1994 showed no attack.

CHLORINATED HYDROCARBONS
Application
EDC/VCM
Country
Norway
Size
20 x 2 mm
Service conditions
HCl Tower overhead condenser.
Previous experience
3RE60 failed due to pitting in the haz of badly executed welds.
Sandvik SAF 2205
In service since 1984.
Application
Country
Size and quantity
Service conditions

Previous experience
Sandvik SAF 2205

EDC/VCM
Sweden
3" Sch 40, 250 m
Tube side
Water
Temperature max 90C (194F)
Pressure 2 bar
Shell side
Emulgator, vinylacetate, ethylen
vinyl chloride, organic acids, etc.
Temperature up to 80C (176F)
Pressure max 120 bar
Unknown.
Installed in 1985.

13

Application
Country
Size
Service conditions
Previous experience
Sandvik SAF 2205

PVC
Italy
20 x 2 mm
PVC granules
Previous material failed due to erosion corrosion.
SAF 2205 installed in various exchangers since 1985, replacing
old material.

Application
Country
Size and quantity
Service conditions

EDC/VCM
Taiwan
4" Sch 40, 1300 m
Tube side
Cooling water
Temperature norm. 145C (293F)
Pressure norm 3 bar
Temperature max 200C (392F)
Pressure max 16 bar
Shell side
EDC, C2H2, O2, HCl, CO, CO2, N2,
CuCl2, Al2O3 catalyst
Outlet 250-300C (482-572F)
Inlet 100-250C (212-482F)
Pressure max 2 bar
Unknown.
Delivered September 1987.

Previous experience
Sandvik SAF 2205

Application
Country
Size and quantity
Service conditions
Previous experience
Sandvik SAF 2205

14

VCM
Norway
1" and 2" Sch 80, 150 + 60 m (490 + 195 ft), plate and flanges
Fluidized bed in oxy-chlorination reactor
Temperature 170C (338F)
C-steel and Alloy 825 eroded after 6-12 months.
Installed in 1982, and improved service life compared with
previous materials.

Application
Country
Size
Service conditions

Condenser
USA
22.25 x 1.25 mm
Tube side
Brackish water
Tmax = 65C (149F)
Shell side
Gases with methylene chloride, some HCl and
moisture condensing at 65C (149F)

Previous experience

AISI 316L showed pitting attacks through the tube wall


after 812 months.

Sandvik SAF 2507

Installed in 1993.

SEAWATER COOLING
Application
Seawater Cooler
Country
France
Size
19.05 x 1.24 mm
Service conditions
Tube Side
Chlorinated seawater
T 20-50C (68-122F)
Shell Side
Ethylene oxide
Tin 100C (212F)
Previous experience
Replacement of bimetallic tubing.
Sandvik SAF 2507
Delivered 1991. Tubes still operating perfectly in March '97.

Application
Country
Size
Service conditions
Previous experience

Sandvik SAF 2507

Application
Country
Size
Service conditions

Previous experience
Sandvik SAF 2507
Application
Country
Size
Service conditions

Previous E
experience
Sandvik SAF 2507

Application
Country
Size
Service conditions
Previous experience
Sandvik SAF 2507

Application
Country
Size
Service conditions

Previous experience
Sandvik SAF 2507

Shipboard Seawater Condensers


United Kingdom
19.05 x 1.65 mm
Tube Side
Seawater up to 50C (122F)
Shell Side
Liquified Petroleum Gas at 18 bar
Coated LT C-steel and 316L both failed within 12 months.
Particular problems due to sand in the cooling water in shallow
waters.
First order 1992. Due to good performance SAF 2507 specified
for the whole fleet of 9 vessels.
Product Coolers
Indonesia
25 x 2 mm
Tube Side
Intermittently chlorinated seawater
Tin 29C (84F)
Tout 39C (102F
Shell Side
Reformed gas
Tin 113C (235F)
Tout 40C (104F)
New project.
Tubes delivered 1996 to fabricator. Plant start up 1997.
Seawater coolers
Singapore
19.05 x 1.65 mm
Tube Side
Chlorinated seawater
Tmax 45C (113F)
Shell Side
Low concentration organic acids
New plant.
SAF 2507 selected in preference to 90/10 CuNi because a high risk
of erosion corrosion due to sand in the coolant. Plant start up Jan. 97.
Seawater Coolers
Aruba
19.05 x 1.65 mm
Tube Side
Seawater polluted with sulphides
Shell Side
Hydrocarbons
CuNi failed within 2 months due to the sulphide polluted
seawater.
Specified in preference to Titanium due to possibility of
retaining tubesheets and baffles in CuNi. Tubes delivered 1995.
Effluent Cooler
Australia
19.05 x 1.65 mm
Tube Side
Hydrocarbons + 1.7% H2S, traces of
ammonia and water.
Tin 138C (280F)
Tout 40C (104F)
Shell Side
Seawater
Tin 27C (81F)
Tout 37C (99F)
(estimated metal skin temperature 44C (111F)
AISI 317 failed due to localised corrosion in 2 weeks.
A second bundle failed after 6 months.
SAF 2507 installed Sept 89. Still in perfect order when
inspected in November 1991.

15

OTHER AREAS
Application
Country
Service conditions

Previous experience
Sandvik SAF 2205
Application
Country
Size and quantity
Service conditions

Previous experience
Sandvik SAF 2205

Application
Country
Size and quantity
Service conditions

Previous experience
Sandvik SAF 2205
Application
Country
Size and quantity
Service conditions

Previous experience
Sandvik SAF 2205

16

Ethanol
Italy
1) Vacuum separator: solution of ethanol, NaCl
(max 22.4%) and water at 82C (180F)
2) Separator (3rd effect): solution of ethanol, NaCl
(max 17%) and water at 63C (145F)
3) Heat exchanger (3rd effect): tube side has ethanol with
max 17% NaCl and H2O and temperature of
63C (145F). Ethanol+steam on shell side.
4) Separator-distillator: Tube side with 14% NaCl and water at
60C (140F). (4th effect) on the shell side similar solution at
44C (111F).
New plant.
Delivered in 1983.
Methanol
Canada
19.05 x 1.65 mm, 8000 m
Tube side
Methanol with wet CO2
About 10 ppm chlorides
Inlet 241C (465F)
Outlet 144C (291F)
Shell side
Methanol with Na2CO3
About 70 ppm chlorides
Inlet 85C (185F)
Outlet 115C (239F)
Severe SCC occured on Tp 304 tubes. Only 5 to 6 weeks life
reported.
Delivered in 1982.

Ethylene glycol
Netherlands
19.05 x 2.03 mm, 20,600 m
Tube side
Steam
11.7 bar (170 psi)
Temperature 225C (437F)
Shell side
Acid bleach stream containing glycols and salt
Temperature 175C (347F)
Pressure 4.2 bar (61 psi)
C-steel failed every two years due to corrosion from shell side.
Delivered in 1984
Methanol
New Zealand
19.05 x 1.65 mm, 14 000 m
Tube side
Methanol with wet CO2
10 ppm chlorides
Inlet 241C (465F)
Outlet 144C (291F)
Shell side
Methanol with Na2CO3
70 ppm chlorides
Inlet 85C (185F)
Outlet 115 (239F)
Tp 304 tubes failed after 5-6 weeks due to chloride
induced SCC from the shell side where carbonate scale is formed.
Heat exchanger commissioned in 1983. SAF 2205 was
selected in preference to type 26Cr-1Mo steel.

Application
Country
Size and quantity
Service conditions

Previous experience
Sandvik SAF 2205
Application
Country
Size
Service conditions

Cyanamid acrylamide
Netherlands
19.05 x 1.65 x 1900 mm, 4430 m
Tube side
Air + steam
Inlet 20C (68F)
Outlet 35C (95F)
Pressure 0.01 bar (0.14 psi)
Shell side
Brackish water
Temperature 27-34C (80-93F)
Pressure 2.5 bar (36 psi)
Tp 304L failed due to pitting and SCC.
Delivered in 1982.

Previous Eeperience

Overhead condensers
Japan
19.05 x 1.2 mm
Tube Side
Seawater
Tin 30C (86F)
Tout 35C (95F)
Shell Side
Hydrocarbons, H2, N2, CO2, H2S
Tin 127C (261F)
Duplex alloy containing 3% Mo suffered from pitting corrosion.

Sandvik SAF 2507

Tubes delivered 1995.

Application
Country
Size and quantity
Service conditions

Phenol formaldehyde reactor condenser


Australia
25.4 x 1.65 mm, 2808 m
Tube side
Vapour
Tin 95 (203F)
Tout 90C (194F)
Shell side
Water
Tin 26C (79F)
Tout 40C (104F)
50 ppm Cl
Unknown.
Installed in May 1988.

Previous experience
Sandvik SAF 2304

Application
Country
Size and quantity
Service conditions

Previous experience
Sandvik SAF 2304
Application
Country
Size and quantity
Service conditions
Previous experience
Sandvik SAF 2304

Phtalic anhydride crystallisation


Italy
33.7 x 1.5 mm, 8418 m + 42000 m
Heating coils in crystallisation reactor
Tube side
Diathermic oil 50C (122F)
Shell side
Reactor is fed with naphtalene, 20C (68F),
which is heated up to 50C (122F) at which
temperature reaction takes place.
Carbon steel had a service life of 5 years in 33.7 x 2 mm.
Delivered in 1987.
Steam condensing vessel
United Kingdom
19.05 x 1.65 mm, 228 m
Tube side
Cooling water
Shell side
Steam
Carbon steel failed due to steam erosion.
In service end of 1987. SAF 2304 was chosen due to its
resistance to SCC.

17

Application
Country
Size and quantity
Service conditions

Previous experience
Sandvik SAF 2304
Application
Country
Size and quantity
Service conditions

Previous experience
Sandvik SAF 2304

Application
Country
Size and quantity
Service conditions

Previous experience
Sandvik SAF 2304

Application
Country
Size and quantity
Service conditions

Previous experience
Sandvik SAF 2205

Application
Country
Size and quantity
Service conditions

Previous experience
Sandvik SAF 2205

18

Maleic anhydride - heat exchanger


USA
19.05 x 1.65 mm, 7350 m
Secondary cooler after the reactor
Tube side
Maleic anhydride
Tin 204-232C (400-450F)
Shell side
Steam condensate containing some chlorides
AISI 316 failed from SCC after 2-3 years service.
Delivered in 1986.
Butyl rubber
United Kingdom
3" Sch 10, 60 m
Transfer line for moist butyle rubber cement crumb from the
dryers to the storage vessels.
Temperature 60-70C (140-158F)
Cl traces
pH 10-14
AISI 316 regularly failed due to SCC.
In service since July 1986.

Fermentation of hydrocarbons
Germany
25 x 2 x 2450 mm, 135 m
Tmax 120C (248F), 1/2 h per day
Tnorm 40C (104F)
Cl 200-500 ppm
pH 3.5-4.5
AISI 316Ti has been tested but failed due to corrosion
fatigue.
Delivered 1987. SAF 2304 was chosen due to excellent
test results.
Phenol
Germany
Heat exchanger tubing
Tube side
Steam
Shell side
90% phenol and water
About 60 ppm chlorides
Slightly acidic
Temperature 70C (158F)
Tp 321 and 316Ti stainless steel failed due to pitting and SCC after
3-4 weeks.
Tubes were installed in early 1984.

Glycerol
Italy
1" Sch 5 & 10, 240 m
Tube side
80% glycerol + water with about
20 000 ppm chlorides.
Temperature max 105-110C (230F)
Flow rate 1 m/s (3.3 ft/s)
Shell side
Steam
Temperature max 140C (284F)
C-steel failed after about 2 years.
Installed in 1982. Plant on stream 1986.

Application
Country
Size and quantity
Service conditions

Previous experience
Sandvik SAF 2205

Application
Country
Size
Service conditions

Sandvik SAF 2507


Application
Country
Size and quantity
Service conditions

Previous experience
Sandvik SAF 2304

Polypropylene glycol
Korea
1 1/2" Sch 10S, 240 m
Tube side
Fresh water with 5 ppm chlorides
Inlet is ambient
Shell side
Polypropylene glycol with some chlorides
Inlet max 130C (266F)
Tp 304 failed due to stress corrosion cracking after a short time.
Replacement in 316 also failed due to the same reason.
Coil with SAF 2205 pipe has been in service since 1982.

Reboiler
USA
19.05 x 1.24 mm
Tube side
Steam
T = 127C (260F)
Shell side
Isopropyl alcohol, water and solids
T = 80-105C (176-221F)
Installed in 1992.
IPA/IPE Reboiler
United Kingdom
19.05 x 1.65 mm, 555 m
Tube side
Mixture of isopropylacetat, isopropylethylene and some water
Shell side
Steam, 120C (248F)
AISI 316 failed due to SCC from shell side.
In service end of October 1987.

19

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