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High Alloy Stainless Steels for

Concentrated Sulfuric Acid
John F. Grubb

ATI Allegheny Ludlum
September 2009
© ATI Allegheny Ludlum 2009

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Boiling and Freezing Temperatures for Sulfuric Acid
350
300
250

degrees C

200
BOILING

150
100

H2SO4 . H2O
H2SO4 . 4 H2O

50
0
-50

FREEZING

-100
0

20

© ATI Allegheny Ludlum 2009

40

60
% H2SO4

80

100
2

Contact Process
• S (s) + O2 (g) → SO2 (g)
• 2 SO2 (g) + O2 (g) → 2 SO3 (g)
(in presence of V2O5)
• H2SO4 (l) + SO3 → H2S2O7 (l)

• H2S2O7 (l) + H2O (l) → 2 H2SO4 (l)
© ATI Allegheny Ludlum 2009

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© ATI Allegheny Ludlum 2009 4 . concentrated (98-100%) sulfuric acid.Improving Energy Recovery • Reaction heat liberated during the manufacture of sulfuric acid is recovered by cooling hot process gases to produce high pressure steam. • This has created a demand for alloys that can reliably withstand corrosion by hot (120-200°C).

particularly in capitalintensive industries such as sulfuric acid manufacturing © ATI Allegheny Ludlum 2009 5 . • Corrosion resistance is not the only consideration that determines material selection. • Cost considerations are always important.Selection of Materials • Selection of materials of construction for various concentrations of sulfuric acid is a balance between the features and benefits of a material versus its capital cost.

4 0.Corrosion Potential of Sulfuric Acid (25°C) 0.5 V sce 0.6 0.2 0.2 -0.3 0 10 20 © ATI Allegheny Ludlum 2009 30 40 50 %H2SO4 60 70 80 90 100 6 .7 0.3 0.1 0 -0.1 -0.

Oxidizing Behavior of Concentrated Sulfuric Acid • M (s) + 2 H2SO4 (l)  MSO4 (s/l) + SO2 (g) +2 H2O (l) • Note that no hydrogen is released © ATI Allegheny Ludlum 2009 7 .

Carbon Steel .Isocorrosion 70 oleum 60 0.13 mm/y degrees C 50 40 30 20 10 0 70 © ATI Allegheny Ludlum 2009 80 90 % H2SO4 100 110 8 .51 mm/y 0.

0 84 86 88 90 92 94 96 98 100 %H2SO4 © ATI Allegheny Ludlum 2009 9 .5 rate.5 38°C 1.Penetration 4.0 27°C 0.Carbon Steel . mm/y 3.0 2.0 3.5 0.0 1.5 49°C 66°C 2.

• NACE recommends the use of stainless steel for handling acids above 99. © ATI Allegheny Ludlum 2009 10 .5% to 100.Stainless Steel • Stainless steels are more resistant to concentrated sulfuric acid than are carbon steels.5% and 80% to 88% concentrations.

• Use of "corrosion resistant alloys" for components such as valves. © ATI Allegheny Ludlum 2009 11 .Stainless Steel • The passive film on stainless steel is harder and much more resistant to flow-induced corrosion than is the iron sulfate film that forms on carbon steels. outlets. and wear plates is advised by NACE SP0294-2006. inlets.

1 0 2 4 6 8 10 12 velocity.Effect of Velocity on Corrosion Rate 99. m/s © ATI Allegheny Ludlum 2009 12 .3% Sulfuric Acid. 102°C 10 corrosion rate. mm/y Ductile Iron S31600 N08020 1 Cast iron S30400 0.

5 99 99. C 200 E-BRITE® 180 304 160 310 (passive) 140 120 100 97 97.13 mm/y isocorrosion 220 (active) Temperature.5 100 % H2SO4 © ATI Allegheny Ludlum 2009 13 .5 98 98.Isocorrosion for Three Stainless Steels 240 0.

• Nickel does not add much resistance to corrosion in this environment. • Molybdenum does improve resistance to somewhat diluted acid (less than 93%). © ATI Allegheny Ludlum 2009 14 .Stainless Steel • Molybdenum does not enhance resistance to corrosion in the highly oxidizing environment of concentrated sulfuric acid.

0 0. 1.03 max 1.00 max balance 15 .07 max 2.00 max balance N08020 0.6-4.0-27.0-26.00 max 0.0-14.75 max 17.08 max 2.00 max 3.75-1.010 max 0.5 ----- S31603 0.00 max 0.0-18.00 3.2 --Ti+Cb 6x(C+N) min.40 max 25.00 ----- S44627 0.20 max 0.0 8xC min.00 max 28.5 0.00-3.50 max 24.Stainless Alloys used for Sulfuric Acid Service (Percents by mass).0 19.0-4.0 2.50 0.00 max 1.5-19.0 10.0 32.06-0.00-3.5 ------- S31008 0.0-22.0 2.3-1.0 1.00 max 1.0-30.40 max 0. UNS C Mn Si Cr Ni Mo Cu Cb S30400 0.20 Fe balance balance balance balance © ATI Allegheny Ludlum 2009 S44735 0.5 8.00 max 1.0-38. 1.50 max 0.75 max 16.0-10.0-21.00 max 19.03 max 2.07 max 2.

Acid Coolers • The use of high chloride cooling water for acid cooling creates a challenging materials selection problem in sulfuric acid plants. • In addition to handling the sulfuric acid. © ATI Allegheny Ludlum 2009 16 . on the water side the alloy must be able to resist pitting. crevice corrosion and stress corrosion cracking caused by chlorides.

• Its combination of acid and water side corrosion resistance offers optimum durability and performance in cooler designs. and provides the most cost-effective cooling system. UNS S44735.Acid Coolers • AL 29-4C® alloy. exhibits the highest resistance to these forms of chloride-induced corrosion as well as exhibiting very low corrosion rates in 98% sulfuric acid. © ATI Allegheny Ludlum 2009 17 .

• 14. • This cast iron is extremely brittle. concentrated sulfuric acid.5% silicon cast iron (UNS F47003) is used for sulfuric acid plant equipment. © ATI Allegheny Ludlum 2009 18 .High-Silicon Alloys • Silicon alloys exhibit high resistance to corrosion by hot.

© ATI Allegheny Ludlum 2009 19 .High-Silicon Stainless Steels • Addition of 5% or more silicon to an austenitic stainless steel greatly improves corrosion resistance to 98% sulfuric acid.

C<0.High-Silicon Stainless Steels • A typical high-silicon material is UNS S30601 (Ni 17. Si 5.5%. • At 50°C.3%. S30601 alloy corrodes faster in 70% sulfuric acid than does conventional 316L stainless steel. Cr 17.015%). • This alloy exhibits accelerated corrosion rates at lower acid concentrations. © ATI Allegheny Ludlum 2009 20 .5%.

• The higher Ni content of the UNS S32615 alloy coupled with its Cu and Mo aids the resistance to process upsets. 2% Cu. 18% Ni.High-Silicon Stainless Steels • UNS S32615 alloy (18% Cr. 1% Mo. © ATI Allegheny Ludlum 2009 21 . 5% Si) exhibits resistance to corrosion in a concentrated sulfuric acid.

and thus being relatively less expensive to produce. which would exhibit a high level of corrosion resistance in a concentrated sulfuric acid environment.High-Silicon Stainless Steels • ATI Allegheny Ludlum identified a need for a material with a relatively low content of alloying elements. © ATI Allegheny Ludlum 2009 22 .

– US Patent 6. • The product developed is the alloy now identified as UNS S38815. an alloy product of the development project that was started.High-Silicon Stainless Steels • In response to this need.036.917 © ATI Allegheny Ludlum 2009 23 .

High-Silicon Stainless Steels • This alloy has the leanest alloy content of any of the high silicon austenitic stainless steels designed for concentrated sulfuric acid service. © ATI Allegheny Ludlum 2009 24 . thereby creating a lower cost material to replace existing alloys.

High-Silicon Stainless Steels • S38815 alloy has about 5% delta ferrite content. to provide enhanced weldability. • Most other high-silicon austenitic alloys are likely to experience weld hot cracking. © ATI Allegheny Ludlum 2009 25 .

0 max 5.0-5.5-8.5-2.0-17.5 13-15 13.0-25.75-1.5 1.50 0.Silicon-Containing Stainless Alloys used for Sulfuric Acid Service (Percents by mass) UNS C Mn Si Cr Ni Mo Cu Nominal Sum Fe S70003 0.8 41.015 max 1.50 41.0 38.5 S30601 0.5-22.00 22.0-11.0 0.020 max 2.0-21.0 max 6.0 8.50 max --- 2.07 max 26 .75-1.6 17-18 17-18 --0.0 0.0 16.0 max 4.0 max 5.8-6.3 balance balance balance balance © ATI Allegheny Ludlum 2009 S32615 0.5-6.3-1.5 47.030 max 2.0 17.35 max S38815 0.5 0.

temperatures are usually limited to about 150°C maximum. • Maximum service temperature is 427°C. Division 1 construction has been approved under Code Case 2450. © ATI Allegheny Ludlum 2009 27 .S38815 Alloy • Use of S38815 material for ASME Section VIII. • For sulfuric acid service.

© ATI Allegheny Ludlum 2009 28 .S38815 Alloy • S38815 alloy is marketed exclusively through MECS Inc. • It exhibits outstanding resistance to corrosion by hot. under the name ZeCor®-Z alloy. concentrated sulfuric acid..

1 mm/y 110 0.2 mm/y degrees C 140 130 120 0.Isocorrosion for ZeCor®-Z Alloy 160 150 0.025 mm/y 90 80 90 92 94 96 98 100 %H2SO4 © ATI Allegheny Ludlum 2009 29 .05 mm/y 100 0.

ZeCor®-Z Alloy Tower Installation © ATI Allegheny Ludlum 2009 30 .

ZeCor®-Z Alloy Grids and Supports © ATI Allegheny Ludlum 2009 31 .

ZeCor®-Z Alloy Acid Distributors © ATI Allegheny Ludlum 2009 32 .

ZeCor®-Z Alloy Mesh Pad © ATI Allegheny Ludlum 2009 33 .

ZeCor®-Z Alloy Piping System © ATI Allegheny Ludlum 2009 34 .

Summary • Concentrated sulfuric acid creates an oxidizing environment that presents unique materials selection challenges. © ATI Allegheny Ludlum 2009 35 . the environment becomes more oxidizing and more corrosive. • As the acid temperature increases.

© ATI Allegheny Ludlum 2009 36 . austenitic stainless steel designed for handling hot. high-silicon. concentrated sulfuric acid. is a weldable. • UNS S38815. concentrated sulfuric acid environments. ZeCor-Z® alloy.Summary • High-silicon alloys exhibit useful resistance to hot.

and increase product purity. ZeCor-Z® alloy. can simplify acid plant construction. © ATI Allegheny Ludlum 2009 37 .Summary • Use of UNS S38815. improve plant life.