Alloy Selection For Service in Sulphuric Acid: A Guide To The Use of Nickel-Containing Alloys
Alloy Selection For Service in Sulphuric Acid: A Guide To The Use of Nickel-Containing Alloys
Alloy Selection For Service in Sulphuric Acid: A Guide To The Use of Nickel-Containing Alloys
FOR A BRIGHTER
FUTURE
Alloy selection
for service in
sulphuric acid
A GUIDE TO THE USE OF
NICKEL-CONTAINING ALLOYS
2
Second Edition
Published 2019
The material presented in this publication has been prepared for the
general information of the reader and should not be used or relied
on for specific applications without first securing competent advice.
Introduction
Commercial concentrated sulphuric acid is one of the This publication describes the behaviour of nickel-containing
most important heavy industrial chemicals. Worldwide alloys and the specific nature of their reactivity with both
consumption is more than 200m tonnes/year. It is sold high and low concentrations, considered separately. The
primarily as 93%, 96% and 98.5% H2SO4, although the behaviour of other metals commonly used in the manufacture
range of “concentrated sulphuric acid” nominally covers or handling of this acid are also discussed. Table 1 lists
the range from 70% to 99+%. Lower acidities, in the range the main nickel-containing alloys and their UNS number
25-70%, are considered to be “intermediate”, or “dilute” considered in this introductory publication. It is not possible
when <25%. Corrosion characteristics of these three ranges to mention all alloys used in sulphuric acid here. A more
of concentration are quite different, only the concentrated detailed discussion of all aspects of materials selection for
product exhibiting the nature of a strongly oxidising acid. sulphuric acid is available elsewhere.1
Table 1 Nominal composition of nickel-containing alloys most are used in sulphuric acid systems
Nickel Institute
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Table 1 con't Nominal composition of nickel-containing alloys most are used in sulphuric acid systems
Nominal composition, % ASTM Spec. b
UNS Seamless
Alloy numbera Ni C Cr Mo Cu Fe Plate tube and pipe
Austenitic stainless steels
304 S30400 8 0.04 18 - - Bal A240 A312
304L S30403 8 0.02 18 - - Bal A240 A312
316 S31600 10 0.04 16.5 2.1 - Bal A240 A312
316L S31603 10 0.02 16.5 2.1 - Bal A240 A312
CF8M J92900 10 0.04 19 2.3 - Bal - -
310 S31000 21 0.05 25 - - Bal A240 A312
20 N08020 33 0.02 19.5 2.2 3.2 Bal A240 B729
CN7M N08007 29 0.04 20 2.3 3.5 Bal - -
904L N08904 24 0.01 20 4.5 1.5 Bal A240 A312
6%Mo c
S31254 18 0.01 20 6.2 0.7 Bal A240 A312
6%Mo c
N08367 24 0.01 21 6.2 - Bal A240 A312
6%Mo c
N08926 25 0.01 20.5 6.2 1 Bal A240 A312
7%Mo S32654 22 0.01 24 7.3 0.5 Bal A240 A312
4% Si d
S30600 15 0.01 17.5 0.1 0.3 Bal A240 A312
5% Si d
S30601 17.5 0.01 17.5 0.1 0.2 Bal A240 A312
5% Si d
S32615 20 0.04 18 1 2 Bal A240 A312
6% Sid S38815 15 0.02 14 1 1 Bal A240 A312
Duplex stainless steel
2205 S32205 5 0.02 22 3.2 - Bal A240 A790
255 S32550 5.5 0.02 25 3.5 2 Bal A240 A790
7-Mo Plus S32950 4 0.03 27.5 2 - Bal A240 A790
CD4MCu J93370 5 0.2 25 2 3 Bal - -
a - UNS numbers beginning with an “N” indicate a nickel alloy, but the definition of a nickel alloy is different than that used by ASTM.
b - in ASTM specifications, most nickel alloys fall into the “B” specifications. However, due to a redefinition of a nickel alloy, a few alloys such as 800
and 20 are being reclassified as stainless steels, and will be included in the “A” specifications. That work is still in progress.
c - the 6%Mo alloys are a series of stainless steels, many of which are proprietary, all with roughly 6%Mo content and roughly equivalent in
performance.
d - the austenitic stainless steels with high Si are proprietary and were developed from nitric acid grades for use in strong sulphuric acid.
The corrosion behaviour of alloys suitable for equipment This publication does not cover concentrations in excess of
used in the manufacture of concentrated sulphuric acid and 99% H2SO4 such as anhydrous, fuming sulphuric acid (i.e.,
in its storage and handling is described. This is followed by “oleum”) or sulphuric acid mixed with other acids, such as
similar information on materials in contact with dilute and nitric acid. A more complete treatment of the use of materials
intermediate strength acid and an introduction to the effects in contact with sulphuric acid of all strengths, in mixtures and
of common contaminants. in the presence of contaminants can be found elsewhere.1
Sulphuric acid manufacture sulphuric acid plant. SO2 at about 425 °C (800 °F) reacts with
The first step in the manufacturing process is the production excess air in the presence of vanadium pentoxide catalyst
of sulphur dioxide (SO2) by oxidation of an available during several passes through the catalyst beds inside the
feedstock. Figure 1, a simplified flow diagram, presents three converter. Since the reaction is highly exothermic, the gases
alternative routes for the generation of SO2. The first of these are passed through gas to gas heat exchangers after each
is combustion of sulphur; the second is recovery of SO2 from pass through the catalyst bed. The SO3 (the anhydride of
metallurgical processes, such as roasting of pyrites and other sulphuric acid) then enters the absorbing towers where
sulphide ores. The third alternative route is regeneration it reacts to form sulphuric acid. About 35% of the heat
from spent acid. Because such acid tends to be contaminated, generated during the process serves to raise the temperature
this process sequence customarily begins with thermal of the sulphuric acid produced. It has been found that, in the
degeneration, followed by scrubbing of the resultant sulphur temperature range 155-190 °C (310-370 °F) relatively low
dioxide prior to cooling and drying. corrosion rates prevail for stainless steels such as Type 304
(S30400) and Type 310 (S31000), for duplex stainless steels
A catalytic converter that is used to form sulphur trioxide such as Alloy 2205 (S32205) and for the high-silicon modified
(SO3) from the SO2 represents the most important part of the 5.5% Si stainless steels.
Sulphur burning
Air filter Drying Compressor Sulphur burning Boiler SO2
Metallurgical
Spent acid
regeneration
Combustion Boiler Scrubbing/cooling Drying Heating
SO2ÆSO3 SO3ÆH2SO4
Nickel Institute
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Figure 2 shows the iso-corrosion curves for some of the Carbon steels
nickel-containing alloys. Cold concentrated H2SO4 is only slightly corrosive to steel
and cast iron, due to the rapid formation of a ferrous sulphate
Stainless steel has replaced carbon steel and cast iron as the (FeSO4) film. However, even moderate flow rates, (>0.6 m/s;
preferred material of construction for converters and acid >2 ft/s) or fluid impingement, can cause the removal of the
coolers. New alloys and the use of anodic protection have protective film and allow corrosion to proceed. Dilution also
increased resistance to corrosion by hot acid. In general, tends to solubilise FeSO4. Elevated temperatures greater than
Type 304L (S30403) is specified for the shell and internals of about 40 °C (105 °F) will also destroy the film and permit
the converter. Drying towers and acid pump tanks are made corrosion. In the case of any of these changed conditions,
from high silicon austenitic stainless steel as an alternative higher alloys would typically be substituted to cope with the
to the traditional brick-lined carbon steel which is still in use. now corrosive conditions. Also, the use of carbon steel may be
Acid piping and coolers are made from high silicon stainless limited by the iron specification in the product acid.
80 C-276
C-22 Unprotected Type 316 is somewhat less resistant than
Alloy 20 Type 304 in hot acid above about 93% because of the
100
316SS 316SS ease of oxidation of the molybdenum component. Table 2
0
0 20 40 60 80 100 provides typical corrosion rates in 99% sulphuric acid at a
Sulphuric acid, % by wt.
temperature of 105-115 °C (220-240 °F) in an absorption rate is reduced from about 5 mm/y (200 mpy) to less than
tower environment. At flow rates of 1.5 m/s (5 ft/s) or more, the 0.05 mm/y (2 mpy).2 Type 316L shell and tube coolers have
corrosion rate for Type 316 increases to more than 7 times that been routinely anodically protected. The limiting temperature
of the molybdenum-free grade, Type 304. The standard cast form for unprotected coolers is about 75 °C (167 °F) while anodically
of Type 316, CF8M (S92900) is appropriate for shut-off valves. protected coolers are used as high as 125 °C (257 °F).4
Nickel Institute
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The Ni-Cr-Mo grades, based on the original Alloy C and Stainless steels
typified by Type C-276 (N10276) are resistant to about 90 °C Martensitic and ferritic grades have almost no application in
(195 °F) in the 93-98% range (with <40 ppm chloride) and dilute acid.
lesser concentrations above 70% to about 50 °C (120 °F).
At moderately elevated temperatures, austenitic grades
Other metals are limited first by concentration. For example, “breakaway
Titanium and zirconium and their alloys are not resistant to corrosion” (i.e., loss of passivation) with a corrosion rate
concentrated acid. >0.12mm/y (>5 mpy) occurs in 0.25% H2SO4 well below 60 °C
(140 °F) for molybdenum-free grades, such as Type 304, but
In the absence of fluoride contamination, tantalum has a about 90 °C (190 °F) in 0.5% acid for Type 316.
reasonable resistance in concentrated acid. It is, however,
subject to initially high corrosion rates and very susceptible Under aerated conditions, however, Type 304 will resist 15%
to absorbing hydrogen with the attendant embrittlement. acid at ambient temperatures. Type 316 will resist 10% acid
under de-aerated conditions, and 30% acid under aerated
Niobium is resistant to concentrated acid under oxidising conditions at room temperature. Corrosion rates under these
conditions, e.g. if oxidising ions are present. It is also resistant conditions can be drastically reduced by the presence of
at all concentrations up to 95% at room temperature. In oxidising contaminants such as cupric, ferric or nitrate ions
concentrated acid, niobium can embrittle. (which enhance passivation) while corrosion is initiated or
increased by reducing species such as chlorides or fluorides.
CORROSION BEHAVIOUR – DILUTE AND
Either stabilised or low-carbon grades must always be used
INTERMEDIATE CONCENTRATIONS
for welded construction because acid in these concentration
Pure dilute sulphuric acid is rarely encountered, it nearly
ranges is specific for intergranular corrosion of sensitised
always contains contaminants of various types and
stainless steel.
concentrations. From 5% to 25%, H2SO4 is a classical
reducing acid, its maximum hydrogen ion (proton) content Certain duplex grades such as 7-Mo Plus (S32950) can resist
occurring at about 25 wt% concentration. From 25% to 5% acid to the boiling point and up to 40% at ambient
70%, the acid gains in oxidising capacity. Over the entire temperatures. The ferrite phase in duplex alloys, in general,
range corrosion characteristics are, however, determined is potentially subject to selective attack in these weak
almost entirely by the nature and concentration of the concentrations.
contaminants present.
Superaustenitic grades of 4% Mo (e.g. Alloy 904L), 6% Mo
The various alloys interact with sulphuric acid in a complex (e.g. UNS S31254, UNS N08367) and the copper-bearing
manner. A single process may involve not only a wide range Alloy 20 offer gradually increasing resistance to intermediate
of sulphuric acid concentrations but also the presence concentrations. In 5% acid at 80 °C (176 °F) both Alloy 904L
of such contaminants as ferric and cupric ions, nitrates, and Alloy 20 showed <0.025 mm/y (<1 mpy) in one test, in
chlorides, ammonia, sulphur dioxide and metallic oxides. another Alloy 20 corroded at 2.3 mm/y (90 mpy) suggesting
These variables exert significant influence not only on the that these alloys are borderline at this temperature.1
oxidising capacity of sulphuric acid solutions but also on the
performance of stainless steels and nickel-bearing alloys in In the presence of severe chloride contamination, even more
contact with them. highly alloyed grades such as Alloy 31 (N08031) or 7% Mo
alloys such as UNS S32654 are now available.
Carbon steels and cast irons
With the exception of the high-silicon cast irons, all Nickel and its alloys
conventional steels and irons are non-resistant to the full Nickel-copper alloys such as Alloy 400 (N04400) can resist
range of weak acid. boiling 5% sulphuric acid (which rapidly loses any dissolved
oxygen) but very high rates of attack are encountered below Other metals
the boiling point. At and above 25%, where the acid becomes Titanium and its alloys are quite readily attacked by dilute
increasingly oxidising in nature, both Alloy 400 and Alloy 200 mineral acids, in the absence of oxidising contaminants and
(N02200) show increasing corrosion rates. are not usually employed.
The Ni-Mo alloys (e.g., Alloy B-2) show good resistance, even Zirconium will nominally resist up to 70% acid at the boiling
in the presence of dissolved oxygen, to about 50 °C (122 °F) point, above which catastrophic “breakaway” corrosion occurs.
and again at the boiling point where the oxygen is removed Welds may, however, suffer preferential attack as low as
by ebullition. Even traces of oxidising contaminants will, 50-60 °C (140 °F). Contaminants in chemical processes
however, cause very severe attack. can lower the critical concentration closer to 60% and, in
the presence of ferric or cupric ions, pyrophoric corrosion
Of the Cr-bearing alloys, Alloy 600 (N06600) has no practical products (a potential hazard for fire or explosion) may form.
application. The Ni-Cr-Mo grades, Alloy C types, can be useful.
In the absence of fluoride contamination, tantalum resists
Alloy C-276 for example, corrodes at less than 0.12 mm/y
0-70% sulphuric acid to the atmospheric boiling point. In
(5 mpy) up to 75 °C (165 °F) in 25% sulphuric acid and up to
fact, reboilers for 70% acid in concentrators are commonly
50 °C (122 °F) at up to 70%. In practical applications, trace
fabricated from tantalum.
amounts of oxidising ions can greatly enhance resistance.
Nickel Institute
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Oxidising ions
The most common oxidant in strong sulphuric acid is nitric
acid, formed from nitrogen in air during the manufacturing
process or from recovery of nitration acids. Passivation of
Type 304 begins in 70% acid at 60 °C (140 °F) when the nitric
acid concentration is about 700 ppm (300 ppm for Type 316).
When Type 304 is activated in anhydrous mixed acids above
about 50 °C (122 °F), however, nitric acid additions increase
corrosion. Figure 3 shows the iso-corrosion data for selected
alloys and the beneficial effects of the presence of oxidising
metal salts.
Figure 3 0.5 mm/y (20 mpy) Iso-corrosion curves for selected alloys Figure 4 Active passive regions for types 304
showing effect of oxidising salts (dotted lines) and 316 stainless steel
°C °F °C °F
200 400
Air-saturated
80 176
Tantalum
150 Boiling point glass
curve Si-iron 300
Type 316
As-mixed
60 140
Type 304
100 Hast B&D
Pb, <80%
200
References
Nickel Institute
Nickel Institute
[email protected]
www.nickelinstitute.org
Published 2019