Sulphuric Acid

High Alloy Stainless Steels for
Concentrated Sulfuric Acid

John F. Grubb
ATI Allegheny Ludlum

September 2009
ATI Allegheny Ludlum 2009
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
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)

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 (120-200C), concentrated
(98-100%) sulfuric acid.
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.
Corrosion resistance is not the only
consideration that determines
material selection.
Cost considerations are always
important, particularly in capitalintensive industries such as sulfuric
acid manufacturing
5
Corrosion Potential of Sulfuric Acid

(25C)
0.7
0.6
0.5
V sce
0.4
0.3
0.2
0.1
0
-0.1
-0.2
-0.3
0
10
20
30
40
50
%H2SO4
60
70
80
90
100
6
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
Carbon Steel - Isocorrosion

70
oleum
60
0.51 mm/y
0.13 mm/y
degrees C
50
40
30
20
10
0
70
80
90
% H2SO4
100
110
8
Carbon Steel - Penetration

4.0
3.5
rate, mm/y
3.0
2.5
49C
66C
2.0
1.5
38C
1.0
27C
0.5
0.0
84
86
88
90
92
94
96
98
100
%H2SO4
Stainless Steel
Stainless steels are more
resistant to concentrated sulfuric
acid than are carbon steels.
NACE recommends the use of
stainless steel for handling acids
above 99.5% to 100.5% and
80% to 88% concentrations.
10
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.
Use of "corrosion resistant
alloys" for components such as
valves, inlets, outlets, and wear
plates is advised by NACE
SP0294-2006.
11
Effect of Velocity on Corrosion Rate

99.3% Sulfuric Acid, 102C
10
corrosion rate, mm/y
Ductile Iron
S31600
N08020
Cast iron
S30400
0.1
0
10
12
velocity, m/s
12
Isocorrosion for Three Stainless Steels

240
0.13 mm/y isocorrosion
220
(active)
Temperature, C
200
E-BRITE
180
304
160
310
(passive)
140
120
100
97
97.5
98
98.5
99
99.5
100
% H2SO4
13
Stainless Steel
Molybdenum does not enhance
resistance to corrosion in the
highly oxidizing environment of
concentrated sulfuric acid.
Molybdenum does improve
resistance to somewhat diluted
acid (less than 93%).
Nickel does not add much
resistance to corrosion in this
environment.
14
Stainless Alloys used for Sulfuric

Acid Service
(Percents by mass).
UNS
C
Mn
Si
Cr
Ni
Mo
Cu
Cb
S30400
0.07 max
2.00 max
0.75 max
17.5-19.5
8.0-10.5
-------
S31008
0.08 max
2.00 max
1.50 max
24.0-26.0
19.0-22.0
0.3-1.5
-----
S31603
0.03 max
2.00 max
0.75 max
16.0-18.0
10.0-14.0
2.00-3.00
-----
S44627
0.010 max
0.40 max
0.40 max
25.0-27.5
0.50 max
0.75-1.50
0.20 max
0.06-0.20
Fe
balance
balance
balance
balance
S44735
0.03 max
1.00 max
1.00 max
28.0-30.0
1.00 max
3.6-4.2
--Ti+Cb
6x(C+N) min,
1.00 max
balance
N08020
0.07 max
2.00 max
1.00 max
19.0-21.0
32.0-38.0
2.00-3.00
3.0-4.0
8xC min,
1.00 max
balance
15
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, on the water side the alloy must
be able to resist pitting, crevice
corrosion and stress corrosion
cracking caused by chlorides.
16
Acid Coolers
AL 29-4C alloy, UNS S44735, exhibits
the highest resistance to these forms
of chloride-induced corrosion as well
as exhibiting very low corrosion rates
in 98% sulfuric acid.
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.
17
High-Silicon Alloys
Silicon alloys exhibit high
resistance to corrosion by hot,
14.5% silicon cast iron (UNS
F47003) is used for sulfuric acid
plant equipment.
This cast iron is extremely
brittle.
18
High-Silicon Stainless Steels

Addition of 5% or more silicon to
an austenitic stainless steel
greatly improves corrosion
resistance to 98% sulfuric acid.
19

A typical high-silicon material is
UNS S30601 (Ni 17.5%, Cr
17.5%, Si 5.3%, C<0.015%).
This alloy exhibits accelerated
corrosion rates at lower acid
concentrations.
At 50C, S30601 alloy corrodes
faster in 70% sulfuric acid than
does conventional 316L stainless
steel.
20

UNS S32615 alloy (18% Cr, 2%
Cu, 1% Mo, 18% Ni, 5% Si)
exhibits resistance to corrosion
in a concentrated sulfuric acid.
The higher Ni content of the UNS
S32615 alloy coupled with its Cu
and Mo aids the resistance to
process upsets.
21

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

In response to this need, an alloy
product of the development
project that was started.
The product developed is the
alloy now identified as UNS
S38815.
US Patent 6,036,917
23

This alloy has the leanest alloy
content of any of the high silicon
austenitic stainless steels
designed for concentrated
sulfuric acid service, thereby
creating a lower cost material to
replace existing alloys.
24

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.
25
Silicon-Containing Stainless Alloys

used for Sulfuric Acid Service
(Percents by mass)
UNS
C
Mn
Si
Cr
Ni
Mo
Cu
Nominal
Sum
Fe
S70003
0.020
max
2.0 max
6.5-8.0
8.0-11.00
22.0-25.0
0.50 max
---
2.0 max
4.8-6.0
16.0-21.0
17.5-22.5
0.3-1.5
1.5-2.5
S30601
0.015
max
1.0 max
5.0-5.6
17-18
17-18
--0.35 max
S38815
0.030
max
2.0 max
5.5-6.5
13-15
13.0-17.0
0.75-1.50
0.75-1.50
41.5
47.8
41.0
38.3
balance
balance
balance
balance
S32615
0.07 max
26
S38815 Alloy
Use of S38815 material for ASME
Section VIII, Division 1
construction has been approved
under Code Case 2450.
Maximum service temperature is
427C.
For sulfuric acid service,
temperatures are usually limited
to about 150C maximum.
27
S38815 Alloy
S38815 alloy is marketed
exclusively through MECS Inc.,
under the name ZeCor-Z alloy.
It exhibits outstanding
resistance to corrosion by hot,
28
Isocorrosion for ZeCor-Z Alloy
160
150
0.2 mm/y
degrees C
140
130
120
0.1 mm/y
110
0.05 mm/y
100
0.025 mm/y
90
80
90
92
94
96
98
100
%H2SO4
29
ZeCor-Z
Alloy
Tower
Installation
30
ZeCor-Z Alloy Grids and Supports
31
ZeCor-Z Alloy Acid Distributors
32
ZeCor-Z Alloy Mesh Pad
33
ZeCor-Z Alloy Piping System
34
Summary
Concentrated sulfuric acid
creates an oxidizing environment
that presents unique materials
selection challenges.
As the acid temperature
increases, the environment
becomes more oxidizing and
more corrosive.
35
Summary
High-silicon alloys exhibit useful
resistance to hot, concentrated
sulfuric acid environments.
UNS S38815, ZeCor-Z alloy, is a
weldable, high-silicon, austenitic
stainless steel designed for
handling hot, concentrated
sulfuric acid.
36
Summary
Use of UNS S38815, ZeCor-Z
alloy, can simplify acid plant
construction, improve plant life,
and increase product purity.
37

Sulphuric Acid

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High Alloy Stainless Steels for

Concentrated Sulfuric Acid

ATI Allegheny Ludlum

Boiling and Freezing Temperatures for Sulfuric Acid

ATI Allegheny Ludlum 2009

H2S2O7 (l) + H2O (l) 2 H2SO4 (l)

Improving Energy Recovery

ATI Allegheny Ludlum 2009

Corrosion Potential of Sulfuric Acid

ATI Allegheny Ludlum 2009

ATI Allegheny Ludlum 2009

Carbon Steel - Isocorrosion

Carbon Steel - Penetration

ATI Allegheny Ludlum 2009

Effect of Velocity on Corrosion Rate

corrosion rate, mm/y

Isocorrosion for Three Stainless Steels

Stainless Alloys used for Sulfuric

ATI Allegheny Ludlum 2009

ATI Allegheny Ludlum 2009

High-Silicon Stainless Steels

ATI Allegheny Ludlum 2009

High-Silicon Stainless Steels

High-Silicon Stainless Steels

High-Silicon Stainless Steels

High-Silicon Stainless Steels

ATI Allegheny Ludlum 2009

High-Silicon Stainless Steels

ATI Allegheny Ludlum 2009

High-Silicon Stainless Steels

ATI Allegheny Ludlum 2009

Silicon-Containing Stainless Alloys

ATI Allegheny Ludlum 2009

ATI Allegheny Ludlum 2009

Isocorrosion for ZeCor-Z Alloy

ATI Allegheny Ludlum 2009

ATI Allegheny Ludlum 2009

ZeCor-Z Alloy Grids and Supports

ATI Allegheny Ludlum 2009

ZeCor-Z Alloy Acid Distributors

ATI Allegheny Ludlum 2009

ZeCor-Z Alloy Mesh Pad

ATI Allegheny Ludlum 2009

ZeCor-Z Alloy Piping System

ATI Allegheny Ludlum 2009

ATI Allegheny Ludlum 2009

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