FREQUENT LEAKAGES ON SULFURIC

ACID PIPING
A SOLUTION TO SULFURIC ACID LEAKAGES IN PIPING

The document contains brief history of sulfuric acid leakages at PL-2 and RCA. It also includes compatibility of various materials
for sulfuric acid service. At the end of the document, possible solutions are stated to address the chronic issue

BY: MUHAMMAD BILAL AWAN

 FREQUENT LEAKAGES ON SULFURIC ACID PIPING
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FREQUENT LEAKAGES ON
SULFURIC ACID PIPING Hydrogen Grooving

A SOLUTION TO SULFURIC ACID LEAKAGES IN PIPING Hydrogen gas is generated
when sulfuric acid corrodes
Frequent leakages from sulfuric acid lines are reported recently. Out of carbon steel along with
all three leakages reported at PL-2 in last twelve months, two were formation of protecting layer
thru 2” elbow and one thru the tee socket weld. Detailed investigation of Iron sulfate. The hydrogen
identified “Hydrogen Grooving” as the main damage mechanism. This gas formed rises towards the
report surface and the passage of
these bubbles over the steel
Hydrogen grooving is common in carbon steel piping handling 98% surface (specially at flow
sulfuric acid at low pressure and ambient temperature for interrupted hindering areas like elbows,
operation. valves, fittings) can scrub off
the week passivation layer of
APPEARANCE/MORPHOLOGY: iron sulfate and result in the
formation of grooves exposing
 Hydrogen grooving has a specific “dove-tail” pattern like localized bare metal.
erosion-corrosion. (Refer figures 1-2, 2-2)
 Usually longitudinal grooves along the direction of flow appear. The grooves can be of varying
width and depth. The loss of
metal in this area occurs at a
CRITICAL FACTORS:
far greater rate than uniform
Hydrogen grooving occurs if following are satisfied; corrosion at the same acid
concentration, pressure and
 Hydrogen gas is present (In our case, Nascent hydrogen is temperature. The striation in
generated thru passivation of Carbon Steel) the metal is called "Hydrogen
Fe(S) + H2SO4 (l) --> FeSO4(s) + H2 (g) grooving".
 Flow velocities are less than 1fps or intermittent flow (In our case,
During periods of normal
flow is intermittent)
flow, the gas bubbles are very
 Concentrated sulfuric acid (>70%)
small and evenly distributed,
CONTRIBUTING FACTORS: and they are quickly carried
downstream along with the
 Presence of air/oxygen aggravates hydrogen grooving (for CS acid, generally without
only). causing a problem to the pipe
 Flow turbulence as in Fittings (elbows, tees, valves, expansions wall. However, when the flow
etc.) or gaps in socket welds is periodically interrupted and
the acid ceases flowing, the
AFFECTED MATERIALS:
gas bubbles accumulate along
the pipe wall in the upper half
 Carbon Steel
of the pipe scrubbing off the
 Cast Iron
protective film along the way.

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 FREQUENT LEAKAGES ON SULFURIC ACID PIPING
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CRITIQUES ON CURRENT LEAKAGES:

A. LEAKAGE THRU ELBOWS:

1. Two elbows have leaked at sulfuric acid lines of PL-2 since plant operation (first leakage on 24th Mach, 2012
and second leakage on 25th May, 2013).
2. Both the leakages of elbows resulted from hydrogen grooving. (Refer figures 1-1, 2-1)
3. Point of leakage was same in both elbows i.e. point where flow film separates outer wall due to turbulence
(Refer figures 1-2, 2-2)
4. Acid line Survey was conducted in June-July 2012 as a recommendation against the first incident of sulfuric
acid leakage at PL-2.
5. Second elbow which suffered leakage in May, 2013 hasn’t show any appreciable thickness loss in last survey.
It shows that corrosion rate gets abnormally high once hydrogen grooving is instigated.
6. TMLs (thickness measurement locations) are marked for thickness survey and thickness is monitored only at
those points as per API 570.
7. Normal scanning point for elbows is different from the point of leakage/attack due to hydrogen grooving.
(Refer figures 1-2, 2-2)
8. Hydrogen grooving demands complete thickness scanning of elbows and fitting s with special attention to
areas of turbulence. (Refer figures 1-2, 2-2)
9. Minimum 80 schedule is recommended for CS on sulfuric acid (Reference: DuPont paper on Sulfuric Acid
Handling) while installed thickness is 40 schedule.
10. Construction material is CS which is highly susceptible to hydrogen grooving specially in case of intermittent
operation.

Typical dove-tail pattern hydrogen

grooving is evident in both elbows.

Fig. 1-1 refers to leakage occurred on

25th May, 2013

Figure 2-2 refers to leakage occurred

on 24th Mach, 2012 Figure 1-1 igure 2-1

In both cases location of leakage was

similar i.e. the point where flow
direction starts changing and
turbulence is triggered causing
hydrogen grooving. (Highlighted by
red circles)

TMLs are normally marked at

locations marked as green circles. Figure 1-2 Figure 2-2

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 FREQUENT LEAKAGES ON SULFURIC ACID PIPING
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B. LEAKAGE THRU SOCKET WELD OF TEE:

1. Leakage occurred thru pin hole in fillet weld rather than base metal. (Refer figure 3-1)
2. Pin hole in fillet weld resulted from creviced generalized corrosion because of insufficient/broken protective
film of iron-sulfate. Generalized corrosion accelerated at this spot because of poor passivation. (Refer fig. 3-2)
3. Welds are not scanned in normal piping thickness survey as per code.
4. Lack of penetration was observed in fillet welds of affected Tee where turbulence tends to occur and iron
sulfate coating doesn’t form well. (Refer figure 3-3)
5. Inadequate fillet welding was observed at the point of leakage (Refer figure 3-4)
6. As per B31.3 gap between pipe end and shoulder of a socket fitting should be 1.5 mm approximately. On the
leakage side this gap was 10 mm. (Refer figure 3-5)

Figure 3-1 Figure 3-2 Figure 3-3

10mm 7 mm

Figure 3-4 Figure 3-5

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 FREQUENT LEAKAGES ON SULFURIC ACID PIPING
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CONCLUSION:

A. LEAKAGE THRU ELBOWS: Leakage occurred because of hydrogen grooving of CS material contributed by
intermittent flow, low thickness and turbulence along fittings. Presence of air/oxygen aggravated the
deterioration rate.
B. LEAKAGE THRU SOCKET WELD OF TEE: Leakage occurred due to generalized sulfuric acid corrosion of
CS weld. Effective passivation film couldn’t form because of turbulence at crevices formed due to;
 Inappropriate gap between pipe end and tee shoulder
 Notches left due to incomplete penetration

ROOT CAUSE ANALYSIS (RCA):

A. RCA FOR ELBOW LEAKAGE:

OK for continuous
Material Carbon steel operation but not for
intermittent operation

CS is not an appropriate
material for H2SO4
Temperature & Pressure
where temeratures
Design considerations breach 100 deg. F

1-3 fps during normal

operation
KF Flow Velocity
Design parameters Velocity breaches 1-3 fps
range during shut off
and turbulence
CF
Adequate for operating
parameters
Thickness
Acid Leakage thru
elbow Inadequate to cater for
hydrogen grooving

Intermittent acid dosing Inspection frequency

Pump operation
(For 1 hr after 3-4 days) inadequate for fittings of
Operational low thickness
Considerations
Inspection Inspection Regime

Guidelines not
Presence of oxygen developed for scanning
Presence of Air/Oxygen elbows at acid service
aggravates deterioration
Environment / Operating
condition
Intermittent acid
Acidic environment injection contributed in
line fitting failure

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 FREQUENT LEAKAGES ON SULFURIC ACID PIPING
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B. RCA FOR FILLET WELD LEAKAGE OF TEE:

OK for continuous
Material Carbon steel operation but not for
intermittent operation
KF
CS is not an appropriate
material for H2SO4
Temperature & Pressure
CF where temeratures
Design considerations breach 100 deg. F

1-3 fps during normal

operation

Flow Velocity
Design parameters Velocity breaches 1-3 fps
range during shut off
and turbulence

Adequate for operating

parameters
Thickness
Inadequate to cater for
hydrogen grooving

Acid Leakage thru fillet Intermittent acid dosing

Pump operation Inspection frequency
weld of Tee (For 1 hr after 3-4 days) inadequate for fittings of
Operational low thickness
Considerations
Inspection Inspection Regime

Guidelines not
developed for scanning
Skill of welder elbows at acid service
Gap b/w pipe end & tee
Fabrication
shoulder
Appropriate Welding

Incomplete penetration

Presence of oxygen
Presence of Air/Oxygen
aggravates deterioration
Environment / Operating
condition
Intermittent acid
Acidic environment injection contributed in
line fitting failure

CONCENRS:

1. Hydrogen grooving has started in all elbows, so they are all prone to excessive corrosion and possible leakage
in near future. On temporary basis, InduMar epoxy resin-based wrappings can be installed on all
elbows/fitting to mitigate chances of leakage.
2. Route of sulfuric acid piping thru piping galleries is above man height posing chances of concentrated
sulfuric exposure to humans.

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 FREQUENT LEAKAGES ON SULFURIC ACID PIPING
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MITIGATION/PREVENTION:

1. A continuous operation having oxygen/air free flow reduces probability of hydrogen grooving.
2. Use of minimum fittings with higher thickness gives better life against hydrogen grooving.
3. Using a better metallurgy can eradicate chances of hydrogen grooving. Following are some of those materials
which can be used for concentrated H2SO4 (Arranged in descending superiority considering flow velocity,
temperature);
a. Piping lined with PTFE
b. Alloy-20
c. SS-316L
d. CS (minimum schedule 80)

POSSIBLE SOLUTIONS:

SHORT TERM SOLUTIONS

# SOLUTION DOABILITY IMPACT
Conduct thickness survey of lines on one year frequency and
1 3 3
fittings on six month frequency.
3 Upgrade thickness of all elbows from 40 to 80 schedules. 3 3
Explore and install InduMar epoxy resin-based wrappings as
4 1 4
mentioned earlier to cater for immediate threats.
Evaluate if oxygen/air can be eliminated from the line during
5 4 3
idle/operational period.
6 Evaluate if intermittent operation can be avoided. 4 3
Procedure to be developed for appropriate installation of socket
7 4 3
fittings.
Procedure to be developed for appropriate scanning of acid
8 4 3
fittings.
LONG TERM SOLUTIONS
Evaluate and re-route (if possible) acid line to reduce exposure
1 1 4
of concentrated acid in case of leakage.
2 Replace all CS fittings with SS316L fittings. 3 4
Upgrade metallurgy of complete acid piping to Alloy20
3 1 5
preferably or SS-316L.

 DOABILITY (in terms of cost and time): 5 for easiest, 1 for most difficult
 IMPACT: 1 for minimum, 5 for maximum

REFERENCES:

1. Rehabilitation of hydrogen grooving in sulfuric acid line, (Sulfuric Acid Today, Spring/Summer 2003)
2. ASM Handbook Volume 16, Sulfuric Acid Plant & Technology Manual
3. Handbook of Sulfuric Acid Manufacturing, By Douglas K. Louie (2nd Edition, Section 16)
4. ASM Hand Book Volume-13, Corrosion
5. DuPont FAQs on Sulfuric Acid Handling,
http://www2.dupont.com/Clean_Technologies/en_US/assets/downloads/Equipment_FAQs.pdf