SRU Problems &Troubleshooting

By:Ahmed S. Omran
M.Sc.Chem. , AMIChemE, MAIChE, ACS Member

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 Introduction
Sulfur Chemistry, Physical properties and Safety.
Importance of SRU troubleshooting.
What can goes wrong?

Conversion loss Vs Pressure Drop.

Problems & Troubleshooting(Case Studies)

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 Sulfur Recovery Chemistry
Sulfur forms over 30
solid allotropes, . -which are
The Claus reaction to convert H2S into elemental
different structural sulfur requires the
modifications
presence of one mole of SO
of an 2 for each
element- twothan
more moles
anyofother
H2S:
(1) 2H2S + SO2 3Sx element.
+ 2H2O Besides S8, S7, which is
more deeply yellow than
S8.components,
To provide that ratio of Analysis of "elemental sulfur"
the first step in the Claus process is
reveals an equilibrium mixture of
the combustion of one-third of the H2S in the feed gas:
mainly S8, but with S7 and small
(2) H2S + 1.5 O2 SO2 + H2O amounts of S6.

Combining equations (1) and (2), the overall process reaction is:
(3) 3H2S +1.5 O2 3Sx + 3H2O

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 Our Scope

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Why
Pollution abatement has
Troubleshooting
become as important as
SRU?
profitability.

Environmental authorities
have shutdown entire
refineries because of sulfur
plant outage.

Performance evaluation is
closely related to the
troubleshooting.
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 Consequences!

Ammonia salts Refractory

plugging damage due to
off WHB/condenser overheat
tubes

Missing
mesh pads Main burner
within damage
condenser

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 What Can Go Wrong?
Pressure Drop? Inadequate conversion of H2S to
liquid sulfur?
CAUSE: CAUSE:
Carbon deposits. Improper air-acid gas ratio.

Leaks in boiler/condensers. Loss of catalyst activity.

Plugged seal legs.

END RESULT(S): END RESULT(S):
Air deficiency or even blown Increased SO2 in the
seal legs. incinerator stack.

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 Inadequate conversion of H2S to
liquid sulfur?
1-Measuring Conversion(Mass Balance):
Claus Reaction:

The mandated Sulfur Recovery is 99.4%;

SRU is designed for 99.6%.

Sulfur Recovery Level=

((Net S from all streams entering the unit)-(S of incinerator emission and sour water)

(Net S from all streams entering the unit)

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2-Measuring Conversion(colorimetric
tube):
Check H2S and SO2 in the final condenser
effluent.

How?

Drger tubes are a simple and reasonably

accurate.

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Steps to calculate the
conversion(approx.):
1. Add the ppm of H2S + SO2.

2. Add 2,000 ppm to the

preceding(this allows for
COS,CS2,Sulfur vapors, and
entrained sulfur droplets).

3. Divide the total ppm of sulfur

as obtained above 300,000.

4. Express the result as percent.

5. Subtract the percent from

100%.

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 Wrong Air Ratio
Air flow too high Air flow too low
Easiest way to lose Environmental issue.
conversion.
Symptoms: Symptoms:
-SO3 is formed in the -Yellowish plume in the
incinerator with a white incinerator.
plume.
-Large amount of fuel is -A high incinerator
required to maintain the temperature coupled with low
incinerator temperature. incinerator fuel use.

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 Combustion Air Control
For best conversion ,the ratio H2S/SO2 is 2:1(Supply sufficient air
to burn 1/3 H2S in the total feed).
This ration is measured in the tails gas from the tail gas coalescer.
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 Reactor Problems
Catalyst deactivation:
Symptoms:
1. It is very to do much harm to the catalyst
without causing excessive pressure drop.

2.If you suspect reduced recovery due to lost

catalyst activity check the temperature rise
across the reactor(Outlet-inlet).
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Check the Temperature profile:

This is a good profile This temperature shift

means the effluent in the
first stage is not reaching
equilibrium.
In the first reactor, sulfur
formation has decreased
30% and overall catalyst
effectiveness has declined.

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 Low Reactor
Feed
Temperatures

cause
Sulfur
Precipitation
on the Catalyst

and cause
may occur
Catalyst and result
Deactivation in
conversion
loss.
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 Troubleshooting
Troubleshooting: Check the operation of the
reheat exchanger upstream of the reactor
with the reduced temperature rise.
Solution: Raise the reactor inlet temperature
about 30F (17 C);this will dissipate the
offending sulfur deposits after few days.
Question: If catalyst
activity has been
irreversibly lost, when
catalyst change may
be considered?
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 COS and CS2
Presence of
hydrocarbons and
CO2 in acid gas

cause
Formation of
COS and CS2 in the
reaction furnace. cause

results in
Increase in SO2
emissions. conversion
loss.

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 Symptoms:
An increase in the SO2 emission
Troubleshooting accompanied by lower than
normal 1st reactor inlet
temperature.

Problem : COS and CS2 in the

reaction furnace.

Solution : Destroy both by

operating the 1st reactor at outlet
temperature of 650F (343 C),so
these compounds are hydrolized
to H2S and CO2.

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Sulfur Fog/Demister Damage
Cause & Problem:
As the unit charge drop the unit converts a lower percentage of H2S to
sulfur.
Sulfur should condense on the walls of the tubes. However ,at low
tube-side gas velocities, the sulfur precipitates in the gas stream
itself; A sulfur fog formed.

Damage to the final condenser demister(or coalescer) may allow

entrained sulfur to escape to the incinerator.

-This can be extensively damaged from sulfur fires during start-up.

Symptoms:
The fog does not drop out of the end of the condenser, much of it
appears as SO2 in the incinerator.

Solution:
Avoid unnecessary unit charge drop. Monitor SO2 emission closely at
unit charge drop.
-Avoid oxygen deficiency during start-ups.

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 When to change a catalyst?
A 4 years desired catalyst life in Barzan SRU.

Damage to catalyst and reduced conversion can

be due to many factors besides lost activity:
carbon deposits, leaking condenser tubes,
damaged support screens, sulfuric acid
formation, or operation at the sulfur dew point.

All these problems are invariably associated with

increasing pressure drop.

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In case of normal With the adequate
pressure drop instrumentation
through the .
available, a firm
catalyst bed, Do decision can
we need to change obtained via a
catalyst during the vertical
unit turnaround? temperature
profile through the
1st catalyst bed

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 When to change catalyst?
90%+ of the reaction
heat is released in top
6 inches(0.5 feet)

If the catalyst
activity
dropped, the
reaction is
shifted down
in the bed.

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 Pressure Drop
It is of utmost importance to watch for high-
sulfur plant pressure drop.
Sulfur plants dont suddenly plug without a
prior pressure drop increase.
However a foresight troubleshooting need
continuous data collection and analysis.
Using the capacity ratio parameter plotted
data can tell a trouble in Claus unit.

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 Where

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 Pressure drop
Throughput2

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Carbon Deposits (Case Study)
What happened?

1.The data plotted in the 2.The plant operators had

previous graph actually not not noticed the increased
assembled until after the in the reaction furnace
catastrophic pressure rise. pressure.

3.Only when they tried to 4.An abnormality had been

increase the acid gas reported in the 30th day, a
charge and ran short of air quantity of hydrocarbon was
skimmed off the amine
blower capacity, did they regenerator reflux drum .When
realize something was the HC sample was drawn, it
amiss. bubbled in the sample container.
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 Light Hydrocarbons had
accidentally entered the
amine regenerator,
along with the rich
amine.

The Some was condensed in

Hydrocarbon the reflux drum, the rest
was stripped remained as a vapor and
overhead. was charged, along with
H2S to the sulfur plant.

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 10 times more air
needed to oxidize a mole
of propane than a mole
of H2S

The black carbon

deposited on the top of
first bed catalyst
resulting in high
pressure drop.

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How it can be determined that the increasing P
is due carbon contamination on catalyst?

1.SO2 Concentration in sulfur plant tail gas is very

low?
Low SO2 is a sign of insufficient air in the reaction
furnace.

2.Are light hydrocarbons accumulating in the amine

regenerator reflux drum?

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Catalyst has Keep carbon Reliable way to
already plugged black from prevent:
with carbon: forming in the Liquid
Over a period of first place: hydrocarbons
time,SO2 react with must be
carbon in a slow This can be
reaction at low achieved by separated from
temperature. better control via reach amine
Maximizing reactor increasing the air upstream of
inlet temperature and
flow(Tail gas amine
SO2 levels will help. regenerator.
Significant (10%) H2S/SO2 ration
reductions in pressure analyzer
drop can take weeks. automatically or
Shutting down and manually by
catalyst change is
more practical.
alerting the
operators).

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Leaks cause pressure drop (Case Study)
What happened?

1.Observing a high 2.They opened a drain on

pressure drop; the plant the condenser with intent
operators had suspected a of drawing off excess sulfur.
plugged condenser sulfur Steam not sulfur,
seal leg discharged from the drain.

4.Six days later ,the plant

shutdown with a giant leak
in the high-pressure boiler
tube sheet.
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 A tube leak in the HP steam boiler can
lead to a DISASTER!

1.The high-pressure water will erode the

metal,and the flow of water into the hot gas
stream will rapidly increase
Crash shutdown is the worst thing
that can happened for SRU! Sulfur
plant should be cleared of sulfur by
2.If the direct reheat line is open, sulfur
burning fuel gas instead of H2S before
precipitates on the catalyst; stopping the gas
a shutdown(either ESD or long-
period).Continue flue gas firing(for
flow through the plant and cant be
longer than 24 hrs) until the molten
sulfur cease to flow from
reestablished
sultrapsTM(and maintain condition
more 4 hrs to confirm sulfur purge).
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 How to identify boiler tube leaks
before its too late?
If both steam production
and outlet temperature
are low and pressure
1.The data plotted in the drop is relatively high;
capacity ratio plot should SHUT DOWN the plant.
2.WhenThere
this happens check
be an early sign as a is a tube leak!
for low steam production
gradual increase in
rate from the HP steam.
pressure drop will appear.
rise.

4.Water(steam) leaks also reduce

3.A low gas outlet conversion of H2S to sulfur. Claus
temperature from this reaction shows that equilibrium
boiler. is shifted to the left as the water
partial pressure increases!

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 Conclusion

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References
1. Lieberman, N. (1987). Troubleshooting natural
gas processing: Wellhead to transmission.
2. Kidnay, A. J., Parrish, W. R., & McCartney, D. G.
(2011). Fundamentals of natural gas
processing (Vol. 218). CRC Press.
3. Zachariah, Michael R., and Owen I. Smith.
"Experimental and numerical studies of sulfur
chemistry in H 2/O 2/SO 2 flames." Combustion
and flame69.2 (1987): 125-139.
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