Sulfur Plant Corrosion Experiences
Wet Elemental Solid Sulfur Corrosion
Chelsey Hart (SemCAMS), Shelley Hittel (SemCAMS)
Presented at the Brimstone Sulfur Symposium, Vail
September 11, 2013 Table of Contents
‘Table of Contents
Executive Summary
Sulfur Condenser Corrosion.
Background of System ..
Unexpected Plant Outage: Sulfur Plant Shutdown Sequence of Evens
‘Second Plant Shutdown ~ Sequence of Events.
Summary.
Corrosion Mechanisms
Literature Review cnn
Failure Report by NDE Lab...
4
Information from Alberta Sulphur Research Ltd. (ASRL) «. 14
Experimental Results of Wet Elemental Sulfur Corrosion Test. Is
Conclusion 16
Works Cited sol
Sulfur Plant Corrosion - Amine Best Practices Group ~ Brimstone Sulfur Symposium 2013 Page 2 Executive Summary
‘A sour gas plant (the “Plant”) had an unexpected plant outage in the middle of a Canadian winter due to failure
of a critical piece of equipment in a processing unit unrelated to the sulfur unit. During the outage, tube leaks in
the sulfur recovery unit (“SRU") 1" Condenser (“I" Condenser”) were found, The 1* Condenser leaks were
plugged while the Plant was down and the 1° Condenser was put back in service when the Plant re-started,
‘After being in service for approximately three weeks the 1" Condenser showed signs that another failure had
‘occurred. ‘The Plant was shut down to investigate. This report examines the most likely cause(s) of the
condenser failures.
During the winter outage it is believed that the 1" Condenser was exposed to an extremely corrosive
environment. When the Plant unexpectedly went down, Operations and Maintenance (O&M) efforts were
focused on critical water based systems of the Plant including steam systems, cooling water, treated water and
steam tracing. Manpower resources were not available to conduct a heat soak on the SRU. The sulfur unit was
allowed to sit idle and cool naturally. Within 72 hours, the process side of the I" Condenser in the sulfur unit
had cooled to ~100°C (212°F). At this lower temperature any liquid sulfur left in the condenser tubes would
have solidified. During this time period there was also a 380kPag (SSpsig) purge steam source at the reaction
furnace fuel gas burner in service. This would have supplied a source of water vapour that would have
condensed and mixed with the elemental sulfur as it froze in the tubes. Based on technical literature, advice
from experts from Alberta Sulphur Research Ltd, and an experiment conducted on site, it was apparent that
when solid sulfur contacts carbon steel in the presence of water, wet elemental sulfur corrosion occurs. This
type of corrosion forms iron sulfide, which was found on the tubes, and this type of corrosion can be extremely
aggressive.
When the leaks were found during the initial winter outage, the corrosion mechanism was not yet known, To
repair the leaks, the tubes were only cleaned a few inches into the tubesheet to allow for proper welding of the
plugs. Neither the I Condenser nor the tubes were completely cleaned, only enough cleaning to conduet the
repairs. Furthermore, after the leaks were plugged, the 1" Condenser was pressure tested with water and the
water was drained but no efforts were made to dry out the I* Condenser. As a result, the condenser was
repaired and waiting for Plant start-up for approximately two weeks. It is suspected that the I" Condenser tubes
continued to corrode due to the wet elemental sulfur corrosion condition existing in the condenser during the
two weeks following the leak test, before the facility was restarted.
As a result of this incident, additional operating procedures have been developed to help address the challenges
of prioritizing work for O&M personnel when unexpected Plant failures and/or SRU failures occur. When
possible, a heat soak should always be conducted on an SRU that will be down for more than a day, especially
in winter conditions. Furthermore, if an SRU is to sit idle for a short time, it is best to keep it hot enough that
liquid water is not present. If a heat soak and hot standby are not possible, then need to ensure all sources of
steam and water into the process side are blocked in to minimize the amount of water present and be prepared
for possible corrosion damage.
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Sulfur Plant Corrosion - Amine Best Practices Group ~ Brimstone Sulfur Symposium 2013, Page 3 Sulfur Condenser Corrosion
Before presenting the findings of this investigation, a basic explanation of the Plant operation is provided.
Background of System
‘The Plant is currently operating one SRU made up of three Claus converter beds and a SuperClaus tail gas uni
‘Acid gas, containing HS and CO, is fed to a Reaction Furnace (RF) where approximately 1/3 of the HS is
combusted to produce SO>. Throughout the Claus section of the sulfur process, H,S and SO; react to produce
elemental sulfur (S,) and water (HO). In this particular Plant, the RF operates at approximately 1100°C /
2000°F. The process gas leaving the RF is cooted in the Waste Heat Boiler (WHB) and then the 1* Condenser
and the heat recovered is used to make high pressure (2550 kPag / 370 psig) steam. In addition to steam, any
elemental sulfur that has been formed so far is condensed ftom the process gas into a liquid sulfur product that
drains to the sulfur pits. The liquid sulfur that is produced into the sulfur pits is then pumped to the Sulfur
Forming area, where a formed sulfur product is made. Downstream of the I" Condenser, there is additional
processing equipment including process gas reheaters, catalyst reactor beds and additional condensers, to
‘maximize the conversion of HS to elemental sulfur.
Elemental sulfur produced from the 1° Condenser is a bright yellow liquid that has a freezing point of
approximately 115°C (239°F). At this stage of the process the liquid sulfur produced will have about 6mol%
HS entrained in the liquid. ‘The liquid sulfur drains (by gravity) from the coalescer side of the 1" Condenser
through two rundown lines to a sulfur pit. Each rundown line is equipped with seal legs to prevent gases
escaping to atmosphere and a sight port so that operations can check on each rundown line to ensure liquid
sulfur is properly draining to the sulfur pit. In order to prevent the liquid sulfur from freezing, the rundown lines
are steam jacketed and the rundown lines are also designed with horizontal and vertical crosses so that the lines
can be “rodded out” if they plug with sulfur. The following figure shows a schematic of the 1“ Condenser.
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Sulfur Plant Corrosion ~ Amine Best Practices Group ~ Brimstone Sulfur Symposium 2013 Page 4 Figure 1. Schematic of 1“ Condenser
Unexpected Plant Out:
{fur Plant Shutdown Sequence of Events
When the Plint unexpectedly shutdown in the midst of a Canadian winter, the sulfur unit was shut down and left
to cool. Based on learnings from previous short term SRU outages, Operations did take actions to rod the liquid
sulfur rundown lines to the sulfur pits to ensure that the condensers were drained as much as possible. However,
due to cold winter conditions, the main focus for the O&M Teams was on keeping the boiler feed water, steam,
cooling water and steam tracing systems operational. Any freezing of these water-based systems has the
potential to cause severe to catastrophic failures of the associated piping and equipment. At the time of the
‘unexpected shutdown, it was expected that the Plant would only be down for a few days,
‘The sequence of events for the SRU as a result of the unexpected gas plant shutdown, is outlined below:
Sequence of Events
Day 0:
* The Plant is shut down due to the failure of critical equipment in Hydrocarbon Liquid Recovery Unit
(CHRU”)
© Operations efforts in SRU limited to rodding out rundown lines from condensers to drain condensers of
sulfur.
‘© Operations attention is focused on critical water-based systems in the plant including water treatment,
steam system, cooling water system, stream tracing systems.
Day 1-3:
a ee RR RR
Sulfur Plant Corrosion - Amine Best Practices Group - Brimstone Sulfur Symposium 2013 Page 5 ‘+ Within 24 hours of the Plant being shutdown the gas temperature in and out of the 1" Condenser had
decreased from the normal operating temperatures of about 280°C inlet and 160°C outlet to about 165°C
inlet and 119°C outlet.
‘+ Within 36 hours the inlet and outlet gas temperatures of the 1” Condenser were at about 133°C and
98°C, respectively.
‘* Within 72 hours the inlet and outlet gas temperatures of the condenser had stabilized at about 100°C
and 96°C , respectively. Since elemental sulfur freezes at approximately 115°C, any sulfur in the
condenser would have been solid in less than 72 hours.
‘© During the first 72 hours there was also purge steam left on to the reaction furnace. This would have
supplied a source of water vapour that would have condensed and mixed with the elemental sulfur as it
froze in the tubes.
Day 4:
+ A low pressure (380kPag / SSpsig)) purge steam source, which is injected into the reaction furnace (RF)
fuel gas burner to prevent plugging, was found to be left on. This steam source had been left on for four
days after the plant was shut down,
© When the steam source was found to be left on, the RF pressure had increased from about 3.7kPag
(0.Spsig) to about 16.4kPag (2.4 psig). The I* Condenser gas inlet and outlet temperatures were also at
about 98°C (208°F) and 93°C (19°F), respectively. At these temperatures any liquid sulfur that
remained in the condenser would have been solid and the water vapour from the steam source would
have condensed. The low temperatures, along with the increase in the RF pressure indicate that the
process side of the condenser was starting to fill up with water.
Day 5:
‘© There was a significant spike in the RF pressure, which is believed to be due to the following
© The seal leg off the WHB was found full of water and the water froze in a section of the
rundown line to the sulfur pit,
© Normally pressure would have built up in the seal leg; however, a valve on the WHB rundown
line was open and pressure built up in the WHB and RF. When this valve was closed the
pressure in the WHB and RF decreased due to water, liquid sulfur and steam spraying out of the
sight port on the rundown line.
Day 6:
© Six days after the plant was shut down, personnel found that there was a water level in the RF on the
furnace side, Due to common piping and no isolation, there was about 6ft water level in the RF, WEB,
1* Condenser, and the first stage coalescer. The water was initially suspected to be coming from leaks
in the WHB; however, further inspection revealed the leak was coming from the 1 Condenser.
'* The boiler feed water (BFW) was blocked in and the water in the WHB/1" Condenser was drained.
Day 7-9:
‘© Water continued to be drained from equipment in the sulfur recovery unit, including the 1" Converter
bed and the 2" Condenser.
Day 10:
ss Group ~ Brimstone Sulfur Symposium 2013 Page 6 * Once the water was drained and blinded, the WHB and 1" Condenser were opened up to determine the
extent of the damage, The following was found:
‘© The inlet tubesheet face of the WHB was found to be in good condition,
‘© The outlet tubesheet face of the WHB had sulfur icicles in the bottom 12 tube rows.
‘©. The inlet tubesheet of the 1" Condenser was found to be in good condition,
‘© The outlet tubesheet of the 1” Condenser had sulfur icicles hanging from approximately 75% of
the tubes.
Day I
* The steam side (shell side) of the WHB was filled with water and no leaks through the tubes to the
process side of the exchanger were found.
‘The water side (shell side) of the 1 Condenser was filled and tube leaks in the I* Condenser were
found.
* A boroscope inspection was completed to identify if additional tubes were plugged with sulfur. A very
large number of tubes were found to be plugged with sulfur at the outlet end of the 1 Condenser.
Day 12-14:
‘* One tube in the 1* Condenser was pulled and sent to a Non-Destructive Evaluation (NDE) lab to have a
failure analysis completed on it. Results of the failure analysis are discussed later in this report.
‘* Once all the leaking tubes were identified, plugs were seal welded into the leaking tubes and the
following repair process was completed:
(©. The entire tubesheet and approximately 2” inside the leaking tubes was sand blasted to bare
‘metal. ‘The condenser tubes were not required to be thoroughly cleaned before the plugs were
seal welded in
© Each tube that was being plugged and the surrounding area (at least 3 tubes circumferentially)
‘was pre-heated with a propane torch to 95°C. The temperature was measured using temperature
sticks and this pre-heat was to help avoid thermal shock and cracking.
(© The plugs were seal welded in place and after welding the area was covered with insulation for
slow cooling,
‘© Wet, black on white magnetic particle testing of the seal welds was completed to ensure there
were no cracks.
Day 15:
‘+ A leak test at a pressure of 2861kPag (41Spsig) for one hour was completed on the 1 Condenser and
WHB using treated water at a temperature of about 25°C (77°F). This leak test identified a few more
leaks, so the 1* Condenser was drained and a few more plugs were seal welded in, following the same
procedure as previously used.
‘+ Another leak test was completed at a pressure of 2861kPag (41 5psig) for one hour on the 1” Condenser
and WHB. This leak test was once again completed using treated water at a temperature of about 25°C
(77°F). This leak test was successful, and then the water from both the WHB and Ist Condenser was
drained. Both the WHB and 1" Condenser were then de-blinded and were prepped for unit start-up.
Day 17 -28:
Sulfur Plant Corrosion - Amine Best Practices Group ~ Brimstone Sulfur Symposium 2013 Page 7 ‘* The 1* Condenser remained in this “cold standby” condition until the rest of the gas plant was ready for
start-up
‘* Ibis key to remember that the I” Condenser was only partially cleaned to conduct the tube leak repairs.
‘There was still solid sulfur in the tubes from the initial shutdown on Day 0.
‘+ Even though the water from the leak test was drained, there still would have been residual water left in
the condenser and entrained in the solid sulfur lying in the tubes.
Day 29:
‘© The Plant was re-started.
After repairs were completed and a successful leak test was performed, both the WHB and the 1" Condenser
were drained of water and then remained off line for another two weeks while further repairs were being
completed in the HRU. As part of the repair procedure for the 1* Condenser, it was only partially cleaned to
allow for welding on damaged the tubes. “The failure analysis results of this 1" Condenser tube, including the
NDE lab report, were not available until the Plant was back online. In hindsight, it is suspected that further
corrosion damage occurred while the 1 Condenser was awaiting the Plant restart due to the remaining presence
of elemental sulfur and water in the I* Condenser.
‘Second Plant Shutdown ~ Sequence of Events
Approximately 3 weeks after the Plant re-started, the SRU started to show signs that there was something,
wrong: The operating pressure in the RF started to increase and the sulfur rundowns on the 1“ Condenser were
showing abnormal flow characteristics. ‘The pressure eventually increased exponentially «ind acid gas could no
longer flow through the unit. As a result, the Plant was shut down. Operations found the 1* Condenser to be
plugged with solid sulfur. The sequence of events leading up to this second outage is outlined below.
Online Day 19:
+ During routine operations checks of the rundown sight ports, the east sulfur rundown line was found to
be plugging off and the maintenance department was asked to help unplug the rundown lines.
+ Only the east sulfur rundown line seemed to be plugged and the west rundown line still had molten
sulfur running through it. (East rundown on condenser outlet; west rundown after demister pad section.)
* The rundown line piping is steam jacketed in order to prevent the molten sulfur from freezing. It was
suspected at this point that there was a steam jacket leak on the east rundown line, which was causing
the plugging. The steam supplies to both rundown lines were turned off and temporary steam tracing
and insulation was installed to prevent freezing,
Online Day 20 - 28:
* After initially rodding out the east rundown line there was a surge of clear water that came out of the
rundown line and then the water coming out decreased to a continuous dribble.
‘+ The west rundown line continued to have yellow molten sulfur flowing through it.
Online Day 29 & 30:
‘Maintenance crews continued to rod out the east rundown line and water continued to be drained.
* The operation of the west rundown line was continually monitored to ensure liquid sulfur was still
flowing
‘Water was also found to be leaking from the condenser inlet flange on the inlet end of the 1 Condenser,
which indicated that there could be a tube leak.
Sulfur Plant Corrosion ~ Amine Best Practices Group ~ Brimstone Sulfur Symposium 2013 Page® ‘A temperature indicator located in the middle of the ducting between the WHB and the 1" Condenser
(Figure 3) was found to have dropped to about 106°C (22°F) from the normal operating temperature of
about 280°C (356°F). Initial conclusion was that this temperature indication was reading incorrectly
‘+ There was an oxygen analyzer sample point in close proximity to the temperature indicator.
Maintenance drilled into the oxygen analyzer sample point and found liquid sulfur and water. This
indicated that the ducting between the WHB and the I" Condenser was plugging off.
Online Day 32:
© At approximately 2:00am the sulfur unit pressure at the reaction furnace increased to the point that acid
gas could no longer flow through the sulfur unit
The Plant was shut down.
Once the condenser was opened up a significant amount of solid sulfur was found to have plugged
approximately 90% of the following:
‘© WHB outlet and ducting (piping) to the 1" Condenser.
The 1" Condenser inlet ducting
The 1" Condenser tubes
‘The 1" Coalescer and demister pad
+ The 1* Coalescer outlet ducting
A preliminary leak test at low pressure was completed to try and determine where the leak occurred. This leak
test identified catastrophic damage to the tubes and seal welds on the tubesheet face. This test also confirmed
that the welds on the plugs from the March outage did not fail and that there was no evidence of tubesheet
cracks.
The 1* Condenser inlet temperature transmitter (14-TI-23) was trended using the data historian. Typically the
inlet temperature should be around 280-290°C. This temperature transmitter is located in the middle of the
ducting between the WHB and the inlet to the Ist Condenser. The temperature started dropping off at around
3:00am on April 24" and was down to a temperature of about 106°C on May 2. Once the temperature drops
below about 115°C, solid sulfur would have formed. Initially when the temperature was found to be around
106°C it was thought that the temperature transmitter was not working properly. Upon further investigation it
was found that the sulfur had built up in the ducting up to where the temperature transmitter is located. It is
suspected that the temperature significantly dropped off when the solid sulfur contacted the temperature
transmitter.
‘The following pictures show the quantity of sulfur found in the Ist Condenser and one of the catastrophic tube
failures.
a ar a ee ere enema tn
Sulfur Plant Corrosion ~ Amine Best Practices Group ~ Brimstone Sulfur Symposium 2013 Page 9 Inlet chamber of the Ist Condenser
Condenser tubes full of sulfur Catastrophic tube failure on west end of condenser
Figure 2. Pictures of Condenser Failure
‘Summary
Once the Plant was re-started after the initial outage, investigation revealed that the RF pressure gradually
increased over a 3-4 week period and near the end of that period, the pressure increased exponentially until gas
could no longer flow. ‘The gradual increase in pressure supports the theory that corrosion was taking place
uring the two weeks after the final leak test forthe initial repair while the suifur unit was waiting on the rest of
the Plant for re-start. It is suspected that there were tube leaks in the condenser at startup. These leaks
‘worsened over the next few weeks until a major failure occurred. The tube leaks were significant enough to
cause the sulfur to condense and cause massive sulfur build up that ultimately restricted acid gas flow through
the sulfur unit
Under normal operation, there is minimal corrosion in the process side of a sulfur unit. In order to have active
corrosion liquid water typically needs to be present. The normal operating conditions of a sulfur unit are always
‘Sulfur Plant Corrosion ~ Amine Best Practices Group ~ Brimstone Sulfur Symposium 2013 Page 10 above the water dewpoint so no liquid water is present. ‘The operating temperatures of the 1" Condenser were
verified and all are parameters were within recommended operating ranges prior to the first failure event. There
is water vapour produced as part of Claus process and there was an additional steam source on to help prevent
the fuel gas burner on the reaction furnace from plugging. As long as the 1" Condenser is operating above the
‘water dew point temperature there would not be any water condensing. There is minimal corrosion occurring in
this case. Even with the additional purge steam that was being introduced, the 1" Condenser was still operating
at temperatures well above the water dew point; therefore, there should not have been any condensed water
formed under normal operating conditions. It is believed that the corrosion occurred when the sulfur unit went
offline without any purging or fuel gas sweep to remove the sulfur from the process equipment and piping.
Corrosion Mechanisms
‘The potential for corrosion of carbon steel to occur in a mixture of solid sulfur and condensed water was further
evaluated, To understand the possible corrosion mechanism occurring, various technical papers were reviewed,
the failure analysis report from the NDE (Non-Destructive Evaluation) lab reviewed and discussions with
Alberta Sulphur Research representatives were held, All of the papers reviewed were published in the Alberta
Sulphur Research Ltd. Quarterly Bulletins or sourced from conference proceedings. Alberta Sulphur Research
Lid, (ASRL) is a highly regarded, world renowned sulfur research organization, which provides expert
independent scientific support to companies interested in understanding the chemistry of sulfur and its
compounds.
Literature Review
In order for corrosion to take place there must be the following four components:
‘+ Anode (+): This is where metal loss occurs and is the portion of the metal that loses electrons (oxidation
takes place).
‘+ Cathode (-):This is where the chemical reaction takes place and is the portion of the metal that gains an
electron (reduction)
‘* Electrical Conductor: This is typically the metal between the anode and the cathode and is pathway for
electrons.
© Electrolyte: This is the solution containing conductive ions, which is often water.
In the case of hydrogen sulfide corrosion (HS) the corrosion mechanism can be represented by the following
equations and diagram (N.I Dowling,’1996):
Anodic; Fe + Fe®* + 2e~
S+2e" > §
Overall: Fe + S > FeS
Steel + Sulfur — Iron Sulfide
a
Sulfur Plant Corrosion ~ Amine Best Practices Group ~ Brimstone Sulfur Symposium 2013 Page 11 Hydrogen Sulfide Corrosion
Figure 3. Hydrogen Sulfide Corrosion Mechanism (Baker Hughes Understanding Production Treating
Chemicals Course Information, 2009)
‘The above corrosion mechanism demonstrates the corrosion of mild steel by H:S. When solid elemental sulfur
is present the corrosion mechanism is known as wet elemental sulfur corrosion. In order for this corrosion
‘mechanism to occur there must be direct contact between steel and solid sulfur and condensed water must be
present (Digby D. Macdonald, 1976). When these conditions exist, the formation of iron sulfide will occur.
Corrosion by wet elemental sulfur can be very rapid. The rate and severity of corrosion depends on the
chemistry and composition of the electrolyte. Some of the corrosion accelerators include the presence of
‘oxygen, HS and elemental sulfur, pH in the range of | to 5, and high temperatures. Work by Alberta Sulphur
Research Ltd. has been completed to determine the effect of wet elemental sulfur corrosion of carbon steel at
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