KNOWLEDGE

FOR A BRIGHTER
FUTURE

Alloy selection for

service in nitric acid

A GUIDE TO THE USE OF

NICKEL-CONTAINING ALLOYS
NO 10075
 2

Alloy selection for service

in nitric acid
(10075)
A GUIDE TO THE USE OF NICKEL-CONTAINING ALLOYS

Second Edition
Published 2020

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.

The Nickel Institute, its members, staff and consultants do not

represent or warrant its suitability for any general or specific use
and assume no liability or responsibility of any kind in connection
with the information herein.

by C.M. Schillmoller, updated by Geir Moe,

edited by Sandra Le Manchet, March 2020

Alloy selection for service in nitric acid

 3

Alloy selection for service in nitric acid

Introduction This publication examines the selection criteria for several

Nitric acid (HNO3) is the second most important industrial stainless steels and nickel-bearing alloys in the production
and handling of nitric acid and in its use, both in the
acid after sulphuric. It is a strong oxidizer and a very
production of ammonium nitrate fertilizers and as an acid
corrosive acid. Even though most stainless steels do not mixture with hydrofluoric acid for descaling.
resist 100% Nitric acid, they are resistant to corrosion by
the 60% to 70% concentrations that result from ammonia/ The Bibliography at the end of the publication contains
air oxidation processes, and the low-carbon or stabilized references that will provide more detailed information on
many of the specific subjects included in this publication.
stainless steels play a major role in the production and
handling of nitric acid over a wide range of temperatures and Table I lists many of the alloys that may be used for nitric
concentrations. acid service.

Table 1 Nominal composition of alloys used in Nitric Acid systems

Nominal composition, % ASTM Spec. b

UNS Seamless
Alloy numbera Ni C Cr Mo Cu Fe Other Plate tube and pipe
Chromium-containing nickel alloys
825 N08825 42 0.03 21.5 3 2.25 30 Ti 0.9 B424 B163
G-30 N06030 Bal 0.02 29 5 1.5 15 (Cb + Ta) 1.0 B582 B622
690 N06690 Bal 0.03 29 - - 9 - B168 B167
C-22 N06022 Bal 0.01 21 13 - 4 W3 B575 B622
C-276 N10276 58 0.01 15.5 16 - 5.5 W 3.5 B575 B622
Ferritic stainless steels
430 S43000 - 0.08 17 - - Bal - A240 -
XM-27 S44627 - 0.05 26 1.2 - Bal Cb 0.12 A240 -
Austenitic stainless steels
304 S30400 8 0.04 18 - - Bal - A240 A312
304L S30403 8 0.02 18 - - Bal - A240 A312
304L NAG S30403 11.5 0.01 18 - - Bal - A240 A312
321 S32100 8 0.04 18 - - Bal Ti 0.40 A240 A312
347 S34700 8 0.04 18 - - Bal Cb 0.50 A240 A312
316L S31603 10 0.02 16.5 2.1 - Bal - A240 A312
317L S31703 12 0.02 18 3.1 - Bal - A240 A312

Nickel Institute
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Nominal composition, % ASTM Spec. b

UNS Seamless
Alloy numbera Ni C Cr Mo Cu Fe Other Plate tube and pipe
Austenitic stainless steels cont'd
310L NAG S31002 20 0.01 25 - - Bal - - A312
800 N08800 33 0.07 21 - - Bal Al 0.3, Ti 0.3 A240 B407
20 N08020 33 0.02 19.5 2.2 3.2 Bal Cb 0.40 A240 B729
4% Si S30600 15 0.01 17.5 0.1 0.3 Bal Si 4 A240 A312
5% Si S30601 17.5 0.01 17.5 0.1 0.2 Bal Si 5.3 A240 A312
5% Si S32615 20 0.04 18 1 2 Bal Si 5.3 A240 A312
6% Si S38815 15 0.02 14 1 1 Bal Si 6 A240 A312
Duplex stainless steel
2304 S32304 4 0.02 23 0.3 - Bal - A240 A790
2205 S32205 5 0.02 22 3.2 - Bal - A240 A790
2507 S32750 7 0.02 25 4 - Bal - A240 A790
329 S32900 3.5 0.04 25 1.5 - Bal - A240 A790
7-Mo Plus S32950 4 0.03 27.5 2 - Bal - A240 A790

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.

NITRIC ACID PRODUCTION conversion to 60–65% HNO3, which is bleached with air
Nitric acid is almost always made by mixing gaseous and sent to storage. Off-gas from the bleaching operation
ammonia with air, converting it to nitric oxide (NO) in a is recycled to the absorber. Some details of the plant lay­
reactor over a platinum-rhodium catalyst at 800–950 °C out may vary, but the basic design is imposed by the nature
(1470–1740 °F), and further oxidizing the NO to NO2. The of the process. Figure 1 is a schematic diagram of a typical
nitric oxide is passed through an absorber column for plant.

Figure 1 Flow diagram of nitric acid plant

some air used for this stream
ammonia-air mixer 8 7 bleach-air
tail gas heater

cooler
tail gas
catalytic burner
combuster (or converter) tail gas water
absorber

1 preheater
ammonia steam 2 turbine
gas heater
3 4 5 6 9
water cooled
air turbine coils
on bubble
burner burner-gas boiler nitric weak column trays
air chamber chamber feedwater acid acid
compressor heater cooler condenser
to atmosphere

EXCHANGER TRAIN concentrated nitric

acid at 8% to 65

Alloy selection for service in nitric acid

 5

The azeotrope of HNO3 and water at atmospheric pressure is to intergranular attack in nitric acid at the heat-affected
67% HNO3. Higher concentrations of acid — 90% to 100% — are zone near welds as a result of sensitization due to the
produced by distilling the dilute acid with a dehydrating agent, precipitation of chromium carbides at the grain boundaries.
e.g., concentrated sulphuric acid, and condensing the fuming
nitric acid vapours from the dehydration tower overhead. Molybdenum additions, found in Types 316L (S31603), and
317L (S31703), are generally considered to improve the
resistance of stainless steels to acid corrosion. However,
CORROSION BEHAVIOUR — MATERIALS
in oxidizing acid, such as nitric acid, Type 304L generally
SELECTION performs better than the molybdenum grades because
Nitric acid is a powerful oxidizing agent as well as an acid. Met- the molybdenum tends to promote the formation of sigma
als and alloys which readily develop protective surface oxides phase, which is less resistant to nitric acid attack. Except in
(such as aluminum, titanium and the stainless steels) are gener-
mixed acids or contaminated nitric acid containing halides,
ally resistant to nitric acid over a wide range of concentration.
Type 304L is preferred to Type 316L for nitric acid service
Stainless steels based on both cost and corrosion resistance.

Nitric acid is a very strong oxidizing medium, and therefore, Selective corrosion along grain boundaries can occur when
chromium content plays an extremely important role in
stainless steels are exposed to strong nitric acid at elevated
corrosion resistance of stainless steels and nickel alloys.
temperatures. Type 304L can be optimized with extremely
Austenitic stainless steels low carbon and low silicon, phosphorus, and sulphur residu-
The most widely used grades of stainless steel for nitric acid als to be extremely resistant to intergranular corrosion after
are the low-carbon or stabilized austenitic grades: Type 304L sensitization. This modified 304L is commonly called 304L
(UNS S30403), Type 321 (S32100), and Type 347 (S34700). Nitric Acid Grade (NAG).
They are resistant to corrosion over a wide range of
For more severe conditions, the higher chromium of 310L
temperatures and concentrations up to 60% nitric acid at the
(S31002) possesses even greater resistance than 304L to
atmospheric boiling point. Figure 2 shows an iso-corrosion
nitric acid concentrations above 60%, as shown in Figure 3.
diagram for Type 304L stainless steel in nitric acid.
Again, the composition and microstructure are optimized,
Stainless steels with higher levels of carbon, such as like 304L NAG, to resist intergranular corrosion at the heat
Type 304 (S30400), that are not stabilized are subject affected zones near welds.

Figure 2 Iso-corrosion diagram for AISI Type 304L stainless steel Figure 3 Isocorrosion diagram of 0.1 mm/y (4mpy)
in nitric acid for some materials for nitric acid service
A 0-0.12 mm/y (0-5 mpy)
°C B 0.12-0.5 mm/y (5-20 mpy) °F °C °F
E C 0.5-1.2 mm/y (20-50 mpy) 140
200 D 1.2-5 mm/y (50-200 mp/y) 400 Ti
D E >5 mm/y (>200 mpy) 120 250
350
C
150 300
Temperature

Temperature

B E 100 200
A 250 310L
B C 80 Boiling point
100 200 150
D curve
A 60 1815LCSi
150 304L
50 100
100 40

50 20 50
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
Nitric acid (wt%) Nitric acid (wt%)

Nickel Institute
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Silicon-bearing austenitic stainless steels The temperature at which the corrosion rate in 65% nitric
Silicon is another element, in conjunction with chromium, exceeds 0.12 mm/y (5 mpy) comparing various duplex steels
that improves corrosion resistance in nitric acid. against Type 304L and 316L is:

A proprietary grade known as 1815LCSi (S30600) contains 203 °C (397 °F) for Type 2304 (S32304)
4% silicon and is remarkably effective in resisting nitric acid 221 °C (430 °F) for Type 2205 (S32205)
>95%. Figure 3 shows iso-corrosion rate curves of 0.1 mm/y 230 °C (446 °F) for Type 2507 (S32750)
(4 mpy) for Types 304L, 310L, and 1815LCSi in nitric 212 °C (323 °F) for Type 304L and 316L
acid. This alloy is used for piping systems and equipment
7-Mo PLUS® (S32950) has provided excellent service in nitric
involving highly concentrated nitric acid at temperatures up
acid tube-side and shell-side cooler condensers operating at
to the boiling point and is commonly used for 98% nitric acid
low to intermediate temperatures. In the Huey test, S32950
transport tanker trucks and storage tanks.
had a corrosion rate of about 0.17 mm/y (7 mpy) compared
Other proprietary stainless steels containing 5% Si, such as to Type 304L which had a corrosion rate of 0.25 mm/y
S30601 and S32615, and a 6% Si alloy, S38815 have been (10 mpy). This alloy also offers useful resistance to chloride
developed for even more severe conditions in concentrated stress-corrosion cracking (SCC) making it a better candidate
acid. Figure 4 shows the beneficial effect of silicon on the than Type 304L or 316L for nitric acid condenser/coolers
corrosion resistance of austenitic stainless steels in boiling cooled with chloride-containing waters.
concentrated nitric acid.
A cautionary note – Ferrite in duplex alloys converts to the
Duplex stainless steels nonmagnetic sigma phase when exposed to temperatures in
Duplex stainless steels possess a mixed microstructure the sensitizing range and sigma phase is severely corroded
containing approximately equal amounts of austenite and by nitric acid. This mitigates against the use of welds and
ferrite phase. This duplex structure results in higher strength as weld repairs of duplex alloys for nitric acid service if the
compared to austenitic grades. welding or service conditions are such that substantial
levels of sigma phase would be formed. Also, use of duplex
Type 2304 (S32304) duplex stainless steel is being used is restricted to temperatures below 260 °C (500 °F) due to
successfully in nitric acid applications in chemical plants. alpha prime precipitation.

Ferritic stainless steels

Figure 4 Influence of silicon content on the corrosion of Cr/Ni steels
in boiling highly concentrated nitric acid. Ferritic grades with 17% Cr or more, exemplified by Type 430
(S43000), were commonly used in nitric acid production
10.0 and are still occasionally used. The corrosion resistance
of Type 430 is generally good except in very strong acid.
Its corrosion resistance is similar to Type 304. However,
fusion welding reduces both the corrosion resistance and
Corrosion rate (mm/y)

1.0
the ductility in the heat-affected zone. Because of welding
problems ferritic stainless steels have, in general, been
replaced by austenitic grades.
0.1
Superferritic stainless steels with high chromium contents,
low interstitial content and low carbon levels, such as XM‑27
(S44627) possess excellent resistance to hot nitric acid.
0.01 However, due to welding difficulties noted for Type 430, they
1 2 3 4 5 6 are generally only available in thin sections, but can be used
Silicon content (%) for heat exchanger tubing.

Alloy selection for service in nitric acid

 7

Higher alloyed stainless steels and nickel alloys Zirconium is better than titanium in 65–90% acid and
Higher alloy materials such as Alloy 20 (N08020), Alloy C-276 finds application under the most severe conditions of
(N10276), Alloy C-22 (N06022), Alloy G-30 (N06030), Alloy concentration and temperature. Zirconium is also used to
690 (N06690), Alloy 800 (N08800), and Alloy 825 (N08825) overcome vapor-phase corrosion, which can be severe in acid
sometimes are used for specific applications in nitric acid reboiler tubing. Zirconium can be subject to stress corrosion
environments, but the less expensive austenitic stainless cracking in nitric acid in concentrations >70%.
steels are usually more economical and just as good. Some
conditions in which higher alloys are useful include high Industrial applications for nitric acid
velocity, mixed acids, or contaminated nitric acid. There are several major markets for nitric acid, all requiring
facilities for storage and handling. It is good engineering
Stainless steels are not recommended for mixtures of nitric practice to use Type 304L stainless steel for storage tanks,
and hydrochloric acid in which the chloride ion induces high
tank trucks, rail cars, piping, valves, and pumps.
corrosion rates and pitting of stainless steels. Nickel alloys,
such as Alloy C-22 and Alloy G-30, exhibit low corrosion rates Nitric acid is used in the production of acrylonitrile textile
in nitric acid with hydrochloric acid concentrations below 10%. fibers (nylons), dyestuffs, and high explosives. Type 304L is
widely used for production equipment in each of these. In
Tubular equipment, such as acid coolers and cooler condens-
nuclear fuel processing, Alloy 825 and Alloy 690 are used to
ers are sometimes problem areas in nitric acid plants. The
handle solvents for dissolving fuel elements of uranium and
cooling media on the water side may contain chlorides and
uranium oxide together with their cladding elements. These
cause SCC in the austenitic stainless steels. Cooler condensers
may present additional problems if the design allows con- solvents include nitric acid up to 45% HNO3 at the boiling
denser acid to migrate to warmer portions of the condenser point, sulphuric acid, and caustic soda.
where it can re-evaporate. Alloy 690 or G-30 may be useful.
The largest industrial application for nitric acid is in the
Other metals fertilizer industry, where it is used to produce ammonium
Silicon cast iron F47003 (containing 14% silicon) possesses nitrate and potassium nitrate. Type 304L stainless steel is
outstanding resistance to nitric acids above 45% concentra- the preferred material for mixers, evaporators, crystallizers,
tions to the atmospheric boiling point. pumps, piping, and tanks. The nitrate is frequently stored
in concentrated solutions of 83% or 92% at 85 °C. Alloy
Aluminum alloys are useful only in concentrated nitric acid 800 or Type 329 stainless steel are sometimes used in heat
(93–100%) at ambient temperatures. Aluminum alloys 1100 exchangers where one might be concerned about SCC.
(A91100) and 3003 (A93003) are frequently used for storage
tanks of concentrated nitric acid >95%. Type 304L stainless
Figure 5 C
 orrosion rate of aluminum A93003 and stainless steel
steel is used for lower concentrations. The effect of nitric
Type 304 in concentrated nitric acid
acid concentration on the corrosion rate of aluminum and
50 304L
stainless steel is shown in Figure 5. 54 °C (130 °F) 1.2

Titanium is highly resistant to nitric acid below 25% and 40 1.0

Corrosion rate (mils/y)

Corrosion rate (mm/y)

in the 65–90% range at the atmospheric boiling point, as Aluminum

30 54 °C (130 °F) 0.8
shown in Figure 3. Type 304L possesses somewhat similar
0.6
corrosion resistance to Titanium up to 60% acid. Above 60% 20
304 0.4
acid, there are other high chromium and high silicon stainless
32 °C (90 °F)
steels which will provide greater corrosion resistance. 10 Aluminum 0.2
Titanium is never used with red fuming nitric acid because a
0 0
pyrophoric reaction can occur. In nitric acid solutions >90%, 93 94 95 96 97 98 99 100
Titanium can be subject to stress-corrosion cracking. Nitric acid (wt%)

Nickel Institute
 8

Mixtures of acids are frequently encountered in chemical and

Figure 6 Nitric acid selection guide
metallurgical processes. A mixture of nitric and hydrofluoric
acids is used in the pickling of stainless steel to remove °C °F
oxide films due to heat treating. Type 304L stainless steel
is inadequate for pickling equipment with a corrosion rate 120 Boiling point curve 250
typically about 25 mm/y (1000 mpy). Alloy 690 exhibits a
corrosion rate of about 0.25 mm/y (10 mpy) and can be used Tantalum
100 Si-iron
for heating coils in this corrosive acid mixture.
200
310L NAG
The addition of nitric acid to sulphuric acid is beneficial for 310Cb Stainless
80 1815LC Si

IMPROVED RESISTANCE
the corrosion resistance of the 18% chromium austenitic
grades. For example, the corrosion rate for Type 304L in
ambient 65% sulphuric acid is about 3 mm/y (120 mpy) but is 150
60
reduced to <0.5 mm/y (<20 mpy) by the addition of about 5% 304L NAG
nitric acid. Temperature
40 Titanium
Figure 6 is a summary diagram to serve as a guide for alloy 304L Stainless 100
selection.

Table 2 shows equipment and suggested materials of 20

Aluminum
construction in a nitric acid plant. 50
67 Azeotrope
Readers seeking more information on any of the subjects 0
covered by this publication should refer to the Bibliography. 0 20 40 60 80 100
Nitric acid (wt%)

Table 2 Equipment and materials of construction for nitric acid

Specific equipment Suggested materials of construction

Ammonia vaporizer Carbon steel
Ammonia storage tanks Carbon steel
Ammonia converter Austenitic stainless steel, nickel alloys
Ammonia converter, cool end 347
Ammonia converter, hot end Nickel alloys
Catalyst gauze Platinum alloy
Catalyst support grid Nickel alloys, highly alloyed stainless steels
NOx absorber 304L
Acid cooler / condenser 304L NAG, 304L, 329, titanium, zirconium 702
Acid concentrator 304L NAG, 7Mo Plus
Distillation column 14% Si cast iron
Concentrated acid cooler High Si austenitic stainless steel, glass-lined steel
Concentrated acid condensers Aluminum, glass/PFTE, high Si austenitic stainless steel, zirconium, niobium, tantalum
Acid mixing tank 304L
65% Acid storage tank 304L
Strong (>93%) acid storage tank Aluminum alloys 3003 or 5056, glass-lined steel

Alloy selection for service in nitric acid

 9

References

1. "Corrosion by Nitric Acid", NACE Publication 5A256, 10. G. Hochoertler and E. M. Horn, "Improvements of Si­
Corrosion, June 1956 bearing Austenitic Stainless Steels for Applications
Involving Highly Concentrated Nitric Acid", A Bayer
2. "Handling Nitric Acid", Chemical Engineering, Nov 11, Report, 1982
1974, pp 129-132
11. J. Husbands and P. K. Whitcraft, "High-Chromium Du­plex
3. Product Information on Stainless Steel for the Nitric Stainless Steel for Nitric Acid Production", Materials
Acid Industry, Vereinigte Edelstahl Werke, TOK3l/08.82 Protection, July 1992
Sandvik Stainless Steel Products Manual for the Process
Industries, Sandvik Steel Company, Tubular Products 12. M. J. Johnson, J. R. Kearns, and H. E. Deverell, "The
Division, May 1985 Corrosion of the New Ferritic Stainless Steels in Nitric
Acid, Corrosion/84, Paper 144, NACE, 1984
4. R. D. Crooks, "Materials of Construction for Nitric Acid",
Process Industries Corrosion, Houston TX, 1986 13. R. Kirchheiner, U. Heubner, and F. Hoffmann, "In­creasing
the Lifetime of Nitric Acid Equipment Using Improved
5. G. L. Delaney and T. F. Lemke, "Corrosion resistance of Stainless Steels and Nickel Alloys", Corrosion/88, Paper
Nickel Alloys in Aqueous Environments", Corrosion 318, NACE, 1988
Australasia, Vol 6, pp 4-6, 1981
14. M. Kobayashi et al, "Development of Nitric Acid Resistant
6. C. P. Dillon, "Corrosion of Type 347 Stainless Steel and Stainless Steels", Corrosion/84, Paper 145, NACE, 1984
1100 Aluminum in Strong Nitric and Mixed Nitric­Sulfuric
Acids", Corrosion, Vol 12, No 5, 1957 15. A. Kratzer et al, "A low Carbon Stainless Steel for Use in
Nitric Acid at Higher Concentrations and Temperatures",
7. C. P. Dillon, "Corrosion of Stainless Steels by Nitric Acid", International Conference on Metallic Corrosion, Val 1,
Materials Protection, July 1992 June 1984

8. M. G. Fontana and N. D. Greene, Corrosion Engineering, 16. D. W. McDowell, "Handling Mixed Nitric and Sulfuric
McGraw Hill, 1967 Acids", Chemical Engineering, Nov 11, 1974, pp 133-135

9. T. Gladman, "A Nitric Acid Grade (NAG) Type 304L 17. D. J. Newman and R. Miller, "Making Nitric Acid in All-
Austenitic Stainless Steel", Materials Protection, Feb 1989 Stainless Plants", Chemical Engineering, July 31, 1967

Nickel Institute
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References

18. C. M. Schillmoller and J. Althoff, "High Technology

Stainless Steels for the Fertilizer Industry", Fertilizer
Industry Annual Review, 1982

19. N. Sridhar, J.B. C. Wu, and S. M. Corey, "The Effect of

Acid Mixtures on Corrosion of Nickel-Base Alloys",
Corrosion/86, Paper No. 182, NACE, 1986

20. M. W. Wilding and B. E. Paige, "Survey on Corrosion of

Metals and Alloys in Solutions Containing Nitric Acid",
ERDA ICP-1107, December 1976

21. Anon, “Heat Recovery at a Nitric Acid Plant,” Result 166

(Sittard, Netherlands: Cadett, 1993), www.portalenergy.
com/caddet/eetb_eut/R166.pdf.

22. Anon, “Serving the Chemical Process and Related

Industries,” (Huntington, VA: Inco Alloys International,
1986), 24 pp.

23. A. I. Asphahani, J. L. Nickerson, “Hastelloy Alloy G-30—A

Specialty Alloy for Applications in the Process Industries,”
Technical Information Sheet No. H-2058 (Kokomo, IN:
Haynes International, 1988), 24 pp.

24. MTI Publication MS-5, “Materials Selector for Hazardous

Chemicals – Nitric Acid”. Materials Technology Institute of
the Chemical Process Industries, Inc., St. Louis, MO (2004).

25. MTI Publication, "Materials Selection for the Chemical

Process Industries", Materials Technology Institute of the
Chemical Process Industries, Inc., St. Louis, MO (2004)

Alloy selection for service in nitric acid

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Nickel Institute
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[email protected]
www.nickelinstitute.org

Published 2020