Nickel alloys for Sulfuric acid production

The contact process that is practically used for production of sulfuric acid in the present time,
was discovered in 1831. Sulfur dioxide is reacted directly with natural oxygen in availability of
platinum catalyst to produce sulfur trioxide.
Most of sulfuric acid units use elemental sulfur as a raw material and some plants use many
sulfur sources including hydrogen sulfide, iron sulfide, sulfur dioxide from metal smelter gases
and waste used and refinery sludge acids. The corrosion issues linked with units employing
these various sulfur sources vary to some extent due to presence of impurities and process
temperatures. Although because contact sulfuric acid units have been processing for a long
time, there have not been several corrosion experiments conducted recently, instead the unit
operators use their long experience in the choosing production materials. A standard diagram
for a double contact absorption sulfuric acid plant is shown in the following figure:

Often sulfur is used in molten state that can be extremely corrosive on the base of
temperature, purity and oxygen magnitude as described in the following table:
Lab corrosion analyses of stainless steel 304 in molten sulfur
Temperature
oC
127
296
368
440

oF
260
565
690
825

Test time
Days
4
2.7
2.7
2

Corrosion rate
Mm/y
0.14
0.13
0.45
1.32

Mpy
5.6
5
17.7
52

Lab corrosion analyses in molten sulfur at 127oC or 260oF

Alloy

Stainless steel

Submerged with some air

inclusion
Mm/y
Mpy
0.08
3.1

Submerged for 24 hours with air

freely included
Mm/y
Mpy
0.25
9.7

304
Carbon steel
Inconel 600
Nickel resist 1
Gray cast iron
Monel alloy
400
Nickel 200

0.10
0.10
0.17
0.19
0.22

3.9
4
6.8
7.6
8.5

1.08
0.27
0.86
1.15
0.91

42.7
10.6
33.8
45.4
36

0.35

13.9

0.78

30.8

On site analysis in Frasch sulfur mining pipes between well ad collection station
Alloy
Hastelloy C
Hastelloy B
Inconel 600
Stainless steel
Stainless steel
Stainless steel
Stainless steel
Gray cast iron
Stainless steel
Carbon steel
Nickel 200

310
317
316
304
430

Corrosion rate
Mm/y
0.02
0.06
0.18
0.46
0.48
0.53
0.94
1.40
1.42
1.98
3.73

Mpy
0.9
2.2
7
18
19
21
37
56
56
78
147

Carbon steel or cast iron is employed to transmit molten sulfur with rapid replacement. Sulfur
is a hygroscopic element that absorbs moisture and produces sulfurous and sulfuric acid.
When remelted, the acid refluxes in carbon steel melting vessel and causes steel apparatus
handling the molten sulfur. Where maintenance is expensive in these equipments, the
probability is of replacement the stainless steels or high nickel alloy like Inconel alloy 600.
Stainless steel 309 and steel 310 have been widely used for the burner nozzles of sulfur
burner and as tube inserts to secure the inlet portions of the waste heat boilers. The dry sulfur
dioxide gas stream downstream of waste heat boiler, could be dealt in carbon steel
considering the corrosion, the blistering and friable corrosion materials produced would soon
plug the catalyst bed of converter. Hence stainless steel 304 is commonly used for hotter
sections of the system and is recommended to aluminum coated steel is another alternative.
In the conditions including steel flexing for example at expansion joints, there is a huge metal
loss. The most vigorous converter, as the temperature of 604oC to 613oC or 1120oF to
1135oF is near the melting point of aluminum utilized to metalize duct, stainless steel 304
should be utilized for expansion joints in duct. Austenitic stainless steels are suitable for this
part of H2SO4 acid unit.
Stainless steel 316L is used for catalyst convenience. The traditional converter is responsible
for one half to the whole pressure fall in sulfuric acid unit and is hence the biggest energy
consumer. Initial catalyst pass is the one subjected to pluggage through corrosion materials
that need downtime for catalyst screening. Stainless steel candles are replaced and recharged
using a crane that is quicker and easier method than removal and replacement of the catalyst
in traditional in-situ bed. However the energy saving design is more occupied by the plants.
To save energy, plant install whole converter and hot gas piping made of austenitic
stainless steel. Heat from exothermic reaction is kept in austenitic stainless steel gas to gas
heat exchanger located in converter. This system and novel design employ warm sulfur
dioxide and sulfur trioxide gases moving among the initial and second catalyst masses to

reheat sulfur dioxide that tracks back to converter. Stainless steel 304, 321, 309 or 310 are
used for this application as per the specific conditions of process. By using a corrosion
resistant nickel stainless steel lighter gauges are used with resultant savings in weight and
manufacturing costs.
Absorption columns are often made of brick lined steel with a membrane and use ceramic
packing. Although, alloys are needed for specific internal hardware like mist eliminators. Often
stainless steel 316, carpenter alloy 20 Cb-3 or Incoloy alloy 825 will be adequate. Often
stainless steel 316, carpenter alloy 20Cb-3 or Incoloy alloy 825 will be adequate. Experience
has shown that elements with structural components of stainless steel 316 have an affordable
life in the top of absorbing towers at temperatures up to about 180oF. At temperatures of
200oF and higher, stainless steel alloy 20 should be utilized, at least for some components,
for suitable life. Corrosion of wires is emphasized by higher acid flows across them causing
higher mist loadings. Hence where mist loadings and temperatures are high, alloy 20 screens
may be utilized in conjunction with other components of stainless steel 316 to receive a
system of intermediate cost and adequate service life.
Although one sulfuric acid plant did not get fully satisfactory service from these alloys and a
corrosion test was run in the space above the packing but below the mist eliminator of
absorber as described in following table:
Alloy

Stainless steel
317
Stainless steel
316
Hastelloy C276
Illium 98
Jessop alloy JS700
Inconel 625
Hastelloy G
Incoloy alloy 825
Carpenter 20Cb-3
Hastelloy B

Corrosion rate
Mm/y
0.03

Mpy
1.1

0.05

2.1

0.11
0.12
0.12

4.4
4.6
4.7

0.17
0.19
0.21
0.25
1.01

6.7
7.6
8.1
9.9
30.8

Highest pit
depth
Mm/y
Mpy
0.10
4

0.13

0.41
0.05
0.20

16
2
8

Pitting took place on several alloys referring that unreported chlorides may have added to the
aggressiveness of the conditions in this specific plant. It seems anomalous that stainless steel
316 was pitted to a lower depth that stainless steel 317. Although the test time was relatively
small and there were several pinpoint pits on stainless steel 316 samples, however there were
some random pits on stainless steel 317 and therefore, the outcomes are understandable on
this basis. Among the wrought materials used, Hastelloy alloy C276 did not show pitting or
irregular corrosion and it was referred as a feasible material of manufacturing in this specific
plant.
Conditions cause to be more destructive in the drying tower where the acid strength is 93% to
94%. Stainless steel 316 can be utilized for the structural components of mist eliminators for
temperatures about 43oC or 110oF however alloy 20 kind materials are recommend at higher
temperatures.
Cast iron serpentine coolers with water cascaded with water cascaded down the outside
utilized to be traditional for quenching both the drying column acid and product acid and

these are sill observed in several other plants. However accomplishing the needed task, cast
iron coolers have several drawbacks, these intake a large land area, water salt deposit on the
tubes needing periodic cleaning, corrosion of the cast iron contaminants the acid product,
there are several flanged joints and leakage, rare cracks and acid losses cannot be ignored,
soil contamination occurs and dilute acid attacks concrete and steel. Moreover the vapor
plume in colder climates may cool on paths and other structures and crate a problem.
Several plants use corrosion resistant nickel based alloys to prevent these problems. One
popular chemical company has successfully used Incoloy alloy 800 tubing in shell and tube
heat exchangers for their concentrated sulfuric acid quenchers. The choice of Incoloy alloy
800 is astonishing at first however it is very popular elevated temperature alloy, it is not
known for resistance to sulfuric acid neither it is stabilized to resist intergranular corrosion in
the heat affected regions of welds. Although annealed seamless tubing was chosen and
dynamic experiments showed it offers outstanding resistance in the concentrated plant. It was
primarily chosen for providing outstanding resistance to chloride ion stress corrosion cracking
due to high nickel concentration, in the chlorine based water that is used for quenching.
Stainless steel 304l is advantageous for use in 98.5% sulfuric acid with a flow speed of six
fps at 88oC or 190oF.
Plate kind coolers have used Hastelloy alloy C276 for quenching 98.5% product acid from
90oC to 70oC with marine water. Besides of resistance to sulfuric acid on the process side,
Hastelloy alloy C276 offers outstanding resistance to seawater and resistance to crevice
corrosion in chloride conditions that is essential in this kind of heat exchanger where an
elastomer produces a strict crevice among the metal plates.
The famous coolers that are used in several new sulfuric acid plants are anodically secured
grade stainless steel 316L and tube heat exchangers. There are several options when
available quenching water has concentrated chlorides or is brackish. An anodically secured
steel 316L is an example. An anodic protection of an air quencher has a problem of throwing
power to secure at least one half the length of the tubes. Another alternative with low quality
quenching water is to utilize a shell and tube cooler using more corrosion resistant alloys such
as Incoloy alloy 825, stainless steel 904L, Hastelloy alloy G and Carpenter alloy. These whole
alloys are presently utilized in anodically secured shell and tube heat exchangers used
brackish water. These alloys offer outstanding resistance to chloride stress corrosion cracking
with high resistance to sulfuric acid.
Sulfuric acid plants that use sludge burning to produce sulfur dioxide have higher corrosion
issues with the carbon steel parts of their process as compare to plants using elemental sulfur
burning for sulfur dioxide production. The magnitudes of waste used and sludge acids
normally vary from 88 to 90% sulfuric acid and 5 to 6% hydrocarbons to 55% sulfuric acid and
1.2% hydrocarbons. Not just are used acids dilute and resulting are more corrosive, even
these have carbon particles that improve the erosion corrosion. To decrease the erosion
effects of particles, fluid velocities are kept low 1.5 m/sec and long radius elbows are utilized
where feasible. The residues burn at higher temperature releasing nitrogen oxides and sulfur
trioxide. When elevated temperatures and unwanted contaminants cause corrosion problems
with carbon steel, stainless steel 304L grade can be successfully employed in many
conditions.
Sulfur dioxide gas streams from metallurgical units comprise of entrained solids that have to
be eradicated in cyclones and scrubbers before introducing into converter. Acid resistant,
brick lined stainless steel 316 cyclones have been utilized to eradicate bigger particles but the
finer dust is still present in gas. Subsequent to quenching, the gas is usually scrubbed with
dilute sulfuric acis in alloy apparatus. The acid content is a function of sulfur trioxide
magnitude in gas and structure water rate. The scrubber water even also contains some

percent of abrasive solids such as 1%. The crevice corrosion, intergranular corrosion in the
heated regions of welds and erosion corrosion have been used in dilute acid scrubbers.
Using corrosion resistant alloys such as stainless steel 304L, stainless steel 316L, Incoloy
alloy 825, stainless steel 904L, alloy 430, carpenter alloy 20Cb3 etc, corrosion can be
controlled.
Entrained acid mist and dust particles in the effluent gas from scrubber should be discarded.
It is often done by passing gas through a wet electrostatic precipitator then contact 93%
sulfuric acid in a drying column filled with ceramic packing. Stainless steel 316L is used to
benefit the ducting among scrubber and electrostatic precipitator, for wires of the precipitator
and to remove attacked carbon steel vessels in these systems.
Downstream of drying portion, H2SO4 unit employing metallurgical stack gases as sulfur
dioxide source is identical to a sulfur burning unit.