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ABPG – Brimstone Sulfur Symposium

Vail - 2012
Presentation hard copy material

I. ABPG Mission – History

See following pages 2 -3

II. ABPG Membership

See following page 4

III. ABPG Member Correspondence: August 2011--Aug 2012

See following pages 5 - 33

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 ABPG MISSION - HISTORY

Mission:

To accumulate a database on amine unit operations and become a clearing-

house for the analysis and distribution of such data to the gas processing and
refining industry on a global basis through articles in trade journals and
through symposiums.

Purpose:

To provide an open forum for exchange of operating experiences for the

purpose of benchmarking, troubleshooting and developing best practices
leading to improved unit operations and reliability.

Scope:

The focus will be primarily issues pertaining to process units that will include
amine treating, sour water treating, sulfur recovery and tail gas treating.

History:

The history of the ABPG is relatively short. It was formed in late 1992 when a group
representing the refining industry, design engineering and an independent
consultant met to discuss the possibility of developing a real-world database for
amine unit operations. The impetus for this initial meeting was a stated interest by
many refiners, both major and independent, in evaluating their amine unit
operations with respect to others in the industry.

The early meetings were devoted to developing an amine unit survey questionnaire
and the ABPG Best Practices Manual. Responses from the questionnaire were the
basis for the 1994 database and includes 75 amine units.

In subsequent meetings, ABPG members analyzed the 1994 database and developed
two articles that were published in industry trade journals. The database was also
the basis for the ABPG Amine Users Symposium held in 1995.

In 1995 ABPG members developed a new survey questionnaire that focused on

amine unit cost control. The results of this survey database were published in the
Summer 1997 issue of Petroleum Technology Quarterly.

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In 1997, the ABPG established a Data Exchange Network (DEN) to provide
members with an open forum to post questions and exchange operating experiences.
Since 1998, ABPG members have met annually to address specific topics of interest
and develop outlines for future articles to be published that focus on issues of
general interest to the industry.

In 2000, the ABPG adopted a focus project to develop a protocol, format and
procedure for standardized amine testing to present to the industry. This effort is
still in progress.

In 2002, the ABPG established a website to host the DEN. Currently, only ABPG
members and ABPG member company personnel have access, but an effort is under
way to make selected DEN data available in the public domain.

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AMINE BEST PRACTICES – MEMBERSHIP ----- August 2012

Title: Member Directory

[ADM-001]:

1. Asquith, Jim – Valero Energy Corporation

2. Bela, Frank – Member Emeritus (formerly Texaco, Shell)
3. Buziuk, Frank – Member Emeritus (formerly Chevron)
4. Crockett, Steven – BP (US)
5. Davis, Jay – Chevron
6. Eguren, Ralph – BP (US)
7. Hatcher, Nate – Member Emeritus (formerly ConocoPhillips)
8. Heeb, Dick – Marathon Petroleum Company LLC
9. Hittel, Shelley – semCAMS
10. Keller, Al – Phillips66
11. Kennedy, Bruce – Member Emeritus (formerly Petro-Canada)
12. Bellinger, Brandon – Flint Hills Resources
13. Schendel, Ron – Consultant
14. Smith, Conrad – DCP Midstream (formerly Duke Energy Field Services)
15. Stern, Lon – Member Emeritus (formerly Shell Global Solutions)
16. Tracy, Frank - Phillips66
17. Tunnell, Duke – Business Manager
18. Way, Bill – EnCana Corporation
19. Welch, Bart – Chevron
20. Young, Mark – Suncor Energy

Updated 24-July-12 // lhs

[ ABPG – Membership.doc ]
LHS/08-08-12

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Amine Best Practices Group

Member Correspondence – August 2011 – August 2012

ARU

ARU-256 HNBR Plate Exchanger Gaskets

ARU-257 Flash Drum Sediment
ARU-258 High MDEA Strength/Loading
ARU-259 THEED
ARU-260 Tandem Seals
ARU-261 HP Rich Amine Sampling
ARU-262 Structured Packing Inspection/Replacement
ARU-263 Rich Amine Filtration Candidate

SRU
SRU-224 Sulfur Transfer Pumps
SRU-225 Incinerator Safety Trips
SRU-226 Loading Arm Seal
SRU-227 Sulfur Pump Trips
SRU-228 Concrete Pit Roof Integrity
SRU-229 SRU Overpressure - API 520 Task Force
SRU-230 Zeeco Burners
SRU-231 Capacity Increase by O2/SO2
SRU-232 Qatar Refractory Dryout Incident
SRU-233 Burner Management Standards
SRU-234 Feed Forward Control
SRU-235 Potential New API Doc - RF/BMS/WHB
SRU-236 Website for the Petroleum Refinery Information Col
SRU-237 SO2 measurements by sulfur customers
SRU-238 Tail Gas Valve Torque

TGT
TGT-056 Quench Column pH Control
TGT-057 Quench Column Filtration & Cooling
TGT-058 Supplemental H2 Quality
TGT-059 Startup with Claus Tail Gas

TGT-060 RGG Cooler Corrosion

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SWS
SWS-030 Water Vapor Calc
SWS-031 Tray Efficiency & Packing HETP
SWS-032 SWS Bottoms Fouling with Elemental Sulphur
SWS-030 Water Vapor Calc

GEN
GEN-034 Fundamentals of Safety
GEN-035 Decommissioning Odorant Tank
GEN-036 Ultrafab H2S Scavengers
GEN-037 HAZOP / PHA Software
GEN-038 Heating Value Analyzers

LLD
LLD-001 TGU Mercaptans
LLD-002 Rich Amine Flash Drum Alarms
LLD-003 Stripped Water pH
LLD-004 Presulfided TGU Catalyst
LLD-005 Rich Amine Emulsions
LLD-006 TGU Booster Blower
LLD-007 Fixed Valve Trays
LLD-008 SO2 Emission Spikes
LLD-009 ARU LOPA
LLD-010 OSHA National Emphasis Program (NEP)
LLD-011 SCOT Catalyst Sulfiding - Problems
LLD-012 Compabloc Lean/Rich Plate Exchangers
LLD-013 Oxygen Line Fire
LLD-014 Sulfur storage pit corrosion
LLD-015 Burner Light-off Sequence
LLD-017 Hythe Plant HAZOP & LOPA
LLD-018 Legal Implications & 2011 LOPA Update
LLD-019 SRU Hot Standby Operation

LLD-020 Startup Lessons Learned

LLD-021 Injury Report of Sulfur Burn

LLD-022 Piping Changes in Active ARU

[ABPG – Aug 2011-Aug 2012 Correspondence Log.doc ]

LHS/08-08-12

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Amine Best Practices Group

Member Correspondence – August 2011 – August 2012

ARU

ARU-257 Flash Drum Sediment

Our fixed-level rich amine flash drum has an underflow weir followed by an overflow
weir, downstream of which the pump takes suction on level control. Solids accumulation
in the vicinity of the underflow weir is sufficient to restrict flow, requiring the operators
to manually adjust the normally-closed suction valve upstream of the overflow weir.
• Has anyone had a similar problem?
• Any advice?

12-15-11

RESPONSES

1) 12-15-11

A shovel. The drum allows iron sulfide particles to settle and it becomes compacted over
time. The compacted solids are difficult to remove without using some force like shovels
or water blasting. On a temporary basis, if you can put a standpipe up through the
nozzle to get above the deposits, that will achieve some short term relief.

2) 12-15-11
Start skimming the flash tank and/or filter the stream that is being treated in the
contactor. Does the amine system have filters in it? Hope the flash tank has a manway!
You might want to sample the solids and find out what is falling apart or being
introduced into the system while you are down.

3) 12-15-11
I don't remember ever hearing of this kind of problem. Maybe your turnaround interval
is longer than ours and we get it cleaned before it gets that bad.

4) 12-15-11
Assuming a packed scrubber on the flash gas, make sure it does not have (or used to
have) carbon steel packing.

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5) 12-16-11

We usually find quite a bit of sludge in the rich amine flash drums at turnaround,
although I don't ever recall it starving the pumps. We don't have Rich filtration.

The problem may be related to the design of your vortex breaker. We usually have a
cage, containing dozens of 1/4" or 3/8" holes, that surrounds the vortex breaker. I've seen
sludge buildup around the cage, but there is always a large gap between the top of the
cage and the hat on the vortex breaker so that a flow path still exists if the cage starts to
plug off.

I've seen stand pipes in towers where the pipe is the suction to a thermosiphon reboiler
but don't recall one in this service. It should help. I can't think of much you could do on-
the-run.

6) Originator, 12-16-11

To clarify, the flash drum has three sections with feed entering the center and skimmed
HCs collecting at the left end. Nominal turnaround interval is five years. At last
inspection we found a mound of sludge as follows:

7) 12-16-11
We have definitely seen sludge buildup in the center compartment, and in some cases
have added provisions for injecting a flush stream directly under the underflow weir.

8) 12-20-11
I have seen only one case of serious sludge accumulation in a gas plant Selexol flash
tank, which had to be shoveled out at turnaround. This was the site where we tested a

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centrifuge for solids removal in a previous post. Unfortunately, the centrifuge was
downstream of the flash tank.

9) 1-4-12
We generally avoid a weir in the amine flash drum. Our contaminants are generally
lighter than the rich amine, so there may be a skimming box but there is generally no
weir. The only suggestion I can offer is to install rich filtration.

10) 1-6-12
Our dirty amine system flash drums don’t have the underflow baffle, only an overflow
for the HC skim – likely not as efficient for separation but avoids the plugging issue you
are experiencing. Could consider cutting slots in the underflow baffle and amine outlet
weir to effectively make one large compartment. If the HC separation becomes an issue
then look into either an inlet gas or rich amine filter/coalescer.

11) 1-6-12

Surprisingly, rich filtration may not be the answer due to failure of the operations folks
to appreciate the importance of solvent hygiene.

When filtering by hole size, all particles smaller than the hole will pass through. Thus,
even full stream filtration operates no differently than slipstream filtration. If particles
must gain size to be filtered by adding more precipitated Fe+2 and S-2, any particles
passing through the filter holes immediately begin weight gain. What better place to
gain the weight than in a nearly stagnant liquid with 30-min residence at the highest
concentrations of both complexed Fe+2 and dissolved H2S – the rich flash drum?

The tendency that defeats rich filtration is that if the filter changes become cumbersome
or expensive, the operations staff may choose to put off filter changes by – ta daa! –
bigger hole size! What this means is that more and bigger particles will go to the flash
drum to become more great big settled particles.

If choosing rich filtration to deal with the problem, the staff has to be committed to
filtering the solution with ever smaller hole sizes in the filter to prevent the particles that
leave the filter from becoming large enough to settle in the flash drum. This will allow
the passing particles a chance to revisit the filter at a size that the filter can remove
without giving them a chance to fall out before being able to return to the filter. The
initial cost of filters and labor may be high, but there will be money saved by reducing
turnaround frequency and turnaround cleaning time and labor.

We are visually misled by rich solutions because they turn dark and show particles faster
than lean solutions. It is misleading because the solution from the sample point for

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either the rich or lean likely has the same particle population and size distribution for a
given filtration hole size. The difference is that the rich amine has much more
precipitating agent concentration (dissolved H2S) available to help the small particles in
the solution grow faster than in the lean solution, giving the appearance of a higher
concentration of particles.

The “smallest hole” filtration strategy can be applied just as well with lean filtration, and
even slipstream filtration, achieving the same results as if applied in the rich filtration
case. I observe in systems filtered by ConocoPhillips technology that the rich solution
will remain much clearer than in systems filtered by conventional filtration because the
ConocoPhillips particle remover is operating at the 0.1-0.5 micron level on a slipstream
versus the 5-70 micron range for most conventional filtration installations.

12) 1-6-12
Your sketch implies sedimentation is greatest at the point of highest velocity, which
baffles me (no pun intended). Perhaps flashing occurs as the result of local pressure
reduction due to the temporary velocity increase as liquid passes under the weir (the
same phenomenon responsible for lift of an airplane wing), causing accelerated
corrosion of the weir compounded by downstream cavitation as the bubbles collapse
upon pressure recovery.

ARU-258 High MDEA Strength/Loading

We are investigating feasibility of debottlenecking by increasing MDEA

strength/loading.
Modeling by two different software systems predicts we can go to 48 wt-% MDEA and
0.5 mole/mole rich loading, with the exception that the low pressure absorbers are
unable to achieve 0.5 m/m.

• Do you have actual data demonstrating stable, reliable operation at these conditions –
i.e.; have the models been validated?
• I am particularly concerned about the effects of increased viscosity in the LPG liquid
treaters.

1-25-12

RESPONSES

1) 1-25-12
We've done this in TGUs at a couple of facilities – I've seen up to 60 wt-% on some
samples and operation has generally been OK, although the towers tended to foam more
often.

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In main systems we have not been able to go that high. I have two refineries that are
running MDEA and one finds that the liquid treater becomes unstable if they go much
over 40 wt-%. The other can't even consistently maintain that strength due to excessive
losses. This system also has a liquid treater which is where I suspect a lot of it is being
lost. They plan to recover the MDEA with a water wash.

When we were designing for an MDEA/DEA blend, the amine supplier indicated
anecdotally that most main systems they see tend to be in the 38-42 wt-% range, whether
the blend or just MDEA. Maybe you can get your amine supplier to show you some
"name withheld" plots of MDEA strength that would show whether anyone is capable of
keeping the strength up consistently. My guess is the ones that can don't have liquid
treaters.

2) 1-25-12
I have one site that normally runs 46-52% MDEA on the refinery main system because
the high pressure GOHT scrubber is circulation-limited and rich loading is routinely 0.5-
0.55 m/m. They have modified some rich piping in this circuit to reduce velocity and
used SS in critical areas. Reliability has been good. The LPG contactor has water wash
and coalescer to recover carryover. LPG temperature is held at 110-125°F.

3) 1-25-12
Our corrosion model shows that rich amine loading should be held below 0.45 for
MDEA. We can easily reach 0.5, but severe CS corrosion results. Fuel gas treaters will
have a problem reaching both high loadings and low H2S in the treated gas. Amine
losses were excessive at high MDEA concentrations until we retrofitted the overhead
KO drum with a water wash.
4) 1-25-12
We have natural gas treating systems that run at 50 wt-% and 0.55 m/m, and sometimes
higher, but I don't think we are doing this in liquid treaters. We still push the envelope
in liquid treaters, I just don't have any quick information. I will almost guarantee you
that corrosion will be a large problem at the high loadings (which come with high
temperatures as well) and you will end up having to install SS in key places, if not
everywhere on the rich side. Amine degradation seems to hasten when operating at high
loadings and high temperatures as well.

5) 1-26-12
Most of my work is also with gas treating using MDEA. We have run MDEA
concentrations to as high as 53% but try to keep at ~50%. Agree the loading should be
kept below 0.5 m/m.

6) 1-27-12
We have several units operating in the 45-50+ wt-% range without any significant issues,
but I don’t have any rich loading data. Accelerated corrosion rates in some of the units

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but was attributed to high bicine levels. We are in the process of gathering data for
simulations to better understand the operation and will update with more info when
available.

7) 3-12-12
We target 50% MDEA in our gas treaters.

8) 4-17-12
The main considerations in a liquid treater are the solvent viscosity and solubility of
heavy hydrocarbons, especially BTEX. I have tabulated these values below for 45 and
55 wt-% MDEA at 100°F and 120°F. 55 wt-% MDEA is quite a bit more viscous and
holds a LOT more BTEX than at lower strength.

ARU-260 Tandem Seals

• What is current practice regarding tandem seals for pumps in the sulfur block – rich
amine, ARU reflux, SWS charge, SWS reflux or pumparound, acid gas KO drum,
etc.?
In the units we have built over the past few years most of these pumps have had tandem
seals, but there is a lack of consistency among different locations. One site might have a
tandem seal in one service while another site will not have a tandem seal in that same
service.

• This is similar to ARU-047, but that was from 10 years ago. Have practices changed
since then?

3-26-12

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 RESPONSES

1) 3-26-12
I would say that environmental standards are much higher now and that double seals are
more frequently required everywhere. We see it more on hydrocarbon service pumps
but of course anytime there is a potential for toxic gas or fires there will be serious
consideration of going the double seal route.

2) 3-26-12
Agree, we also have some with the dry gas seal design, mostly as result of increased
environmental scrutiny.

3) 3-26-12
In general, double seals = standard practice for any scenario that would otherwise result
in H2S emissions.

4) 3-27-12
For > 300 ppmw H2S our standard requires the use of API 682 seal flush plan 74 – dual
pressurized N2 seal.

ARU-263 Rich Amine Filtration Candidate

As seen in the following photos, the rich amine is extremely dirty, yet the lean is
surprisingly clean despite only 10% slipstream filtration. In fact the lean filter inlet
appears almost as clean as the outlet.

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In my simple mind, the filters are doing nothing. So where is all the rich amine black
gunk going? They do report very frequent filter changeouts and lean/rich plate
exchanger cleanouts, and major sludge buildup on tower trays.
• Is it possible their amine system is acting as a lean amine filter before it has a chance
to get to the actual filters?
• How can the filter elements be so plugged, but the lean amine slipstream to the filters
is “clean”?

5-18-12
RESPONSES

1) 5-18-12
Looks like a good case for rich side filtration.

2) 5-21-12
It is common for rich amine to appear dirtier than lean, although not to the extremes in
this case. My understanding is that as H2S is stripped in the regenerator, residual iron is
complexed by amine degradation products that happen to be chelating agents.
According to Jim Jenkins, bicine in particular is a strong chelant.

Despite heavy fouling, I’m sure the % of suspended solids precipitated from solution in a
single pass is insignificant. The lean amine may not be as clean as it looks. In the photo
it appears hazy, suggesting an oil emulsion (naphtha would strip out in the regenerator).
If you tried to read print through the samples, the filter outlet may in fact appear
significantly clearer than the inlet. If they are using polypropylene (or other synthetic-
fiber filter elements), I suggest switching to cotton which has some adsorbency.

I’m having trouble reconciling sludge analyses of (1) 48 wt-% moisture, (2) 47 wt-%
loss on ignition, and (3) 95 wt-% combustible matter. Regardless, iron is only ~ 1.5 wt-
%, so most of the deposit is either organic or elemental carbon. Assuming the former,
most likely both rich and lean contain emulsions which, in my mind, could promote

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effective dispersion of FeS to render the rich opaque, while complexed iron would be
invisible in the lean.

A less likely scenario is that elemental carbon from a heavy oil gasifier accounts for
most of the black particulates in the rich. In my experience, partial ox carbon is likely
hydrophobic and would be extracted by an oil layer which may accumulate in the bottom
of the regenerator. I suggest two simple lab tests:
5) Add hexane or light naphtha to a rich amine sample to see if the black particles tend
to concentrate in the hydrocarbon phase.
6) Filter sufficient rich amine to accumulate a reasonable amount of sludge which can
then be acidified. FeS dissolves, carbon doesn’t.

3) 5-29-12
Sounds like sludge on the trays points to the system doing a pretty fair job of separation
and precipitation of solids – probably need to check the flash tank and the still bottom
head for similar buildups. The reboiler may be fouled as well, and if there is a surge
tank then that may be filling up too.

4) 5-29-12
Remember that filters are for particulate removal and they are probably doing that,
although it may not be visible in the samples. The black "shoe polish" is common in
amine systems and we have seen it come out more in the regenerator towers, but also in
the feed side of the feed/effluent exchangers. It is a mix of some hydrocarbons and
amine. And yes, I agree that this is another application for filtration on the rich stream.

SRU

SRU-227 Sulfur Pump Trips

We have some new units that are having difficulty with sulfur pumps tripping as the unit
rate increases. The plants are attributing the problem to overheating and/or high viscosity
sulfur, but everything is jacketed or ControTraced with 52 psig steam (~ 300°F). The
pumps are vertical Lewis pumps and are installed in a "collection header", not a
conventional concrete pit.

12-6-11

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 RESPONSES

1) 12-6-11
Lewis in particular recommends 35 psig steam to the pump jackets. The pump shaft
bushings are sulfur lubricated, and higher local steam pressure has been found to result in
viscous sulfur within the bushings. See attached bulletin (SRU-227A).

2) 12-6-11
Our Shell Scotford sulfur pumps (degassed sulfur) had lots of problems initially with
Lewis pump bearings overheating. There were some indications of inadequate sulfur
flowing into the bearings. Am not sure if there were any mechanical adjustments made,
since I recall that Lewis initially claimed "all is OK with the pump design." We have
similar pumps at the three new SRUs at Motiva Port Arthur that we will be starting up
around first of 2012. A mechanical person there is supposed to be checking with the
Scotford folks to discuss their issues in greater detail. Will report back to ABPG when I
hear the results.

3) 12-6-11
Check the bearing clearance on the pumps. GAA presented a paper at Brimstone in
2005 (attached excerpt SRU-227B) that discussed sulfur pump overheating/fire issues
solved by increasing the pump bearing clearance from 0.012-0.014" to 0.020". Also
talks about the steam pressure and pump differential expansion problems. We recently
had a pump lock up due to uneven heating of the casing and shaft, but fortunately no
damage.

4) 12-6-11
Have they checked the NPSH available, suction piping geometry and discharge pressure
piping for hydraulic issues? What do the pumps actually trip on? Vibration, bearing
temperature, motor overload, during starts? Is the power supply all checked out as
adequate? If they trip during steady increases in flow rate do the pump curves match the
intended service? I always go back to the basics on these kinds of things.

5) 12-6-11
To prevent the pump lockup I think was described on new unit startups, a Lewis field rep
advised us to leave steam off the pump boot jackets until the sulfur level is two feet
above the pump bowl for 12 hours. Otherwise the boot can grow more than the shaft,
potentially jamming the impellor against the case. However, I saw no such caution in the
Lewis instruction manual on a recent startup.

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6) 12-6-11
We have a similar problem with pumps tripping when % O2 enrichment increases to the
point that sulfur rundown from the first condenser exceeds 330°F, resulting in an average
pit temperature > 300°F. One plant solved the problem by circulating 250°F condensate
through the pump jackets when on O2. In addition to 35 psig steam, one sulfur expert
recommended retrofitting our vertical pumps with 1800 rpm motors.

7) 12-6-11
We had similar issues with Lewis pumps, attributed to overheating. Bearing tolerances
increased friction and pumps tripped and/or caught fire. Lowered steam pressure,
checked bearing clearances and everything has improved.

8) 12-6-11
Attached SRU-227C was presented at Brimstone this last year by a German pump
manufacturer. A fair amount of time was spent discussing bearing clearances and steps
required to prevent overheating. An interesting read.

9) 3-13-12
We were, and to some extent still are, having issues with Lewis sulfur pit transfer pumps
on a new unit tripping with high degassed sulfur temperature. The pumps run
continuously (3600 rpm). We increased bearing tolerances and routed the bearing flush
in parallel, instead of in series. This has helped to keep the pumps from tripping, but the
pumps will still trip if the sulfur temperature reaches ~ 315°F. In the following picture
you can see the tubing that feeds the bearings in parallel.

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SRU-228 Concrete Pit Roof Integrity

A challenge has been raised at one of our refineries about the justification for installing
gratings on top of the existing sulfur pit.

• Do any of you have actual experiences where pit lid failure placed personnel in
danger?

The refinery’s pit lid had deteriorated to the point that rebar was showing where the
concrete had spalled off, and you could indeed see through the holes into the pit. One
argument is that perhaps pit lid deterioration develops over such a protracted period of
time that there would be lots of warnings prior to the pit lid becoming weakened to the
point of endangering personnel.

12-8-11

RESPONSES

1) 12-8-11
The quick answer is no, we haven't had a sulphur pit lid failure, but we are continuing to
monitor the condition of the concrete pit walls. We have noted cracks and holes developing
since the last turnaround inspection. Our oldest concrete sulphur storage pit is 16 years old
with a capacity of 3,000 tonnes. Although we haven't had a failure, I would support the idea
of a grating if access is to be allowed. In our case, we don't permit anyone to walk on the top
of the pit.

2) 12-8-11
Yes, we have had a pit roof failure where a complete section of the roof caved in. This was a
very large pit, maybe 60' x 100', where the roof had been used for both pit access and general
foot traffic. It is currently our recommendation that pit roofs be periodically checked for strength,
and to either minimize or eliminate access. In refineries with small day pits we recommend
installing grating over them where access is required.

3) 12-8-11
We had a couple of pit roofs spall off 2-3" of concrete on the underside and go unnoticed until
pit inspection. Not enough spalling to cause failure, but the risk was certainly there. We have put
down grating on or above some pits to access equipment. We discourage non-essential foot traffic
over pits.

4) 12-8-11
I know of one facility that won't let anyone on the roofs of three particular pits out of concern for
damage. I haven't seen a complete concrete roof failure, but know of several questionable pits that

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no one is allowed on in other plants as well.
_______________________________________________________________________________________

5) 12-8-11
One large Canadian gas plant reportedly had major issues with their pit roof and I understand did
not allow access.

6) 12-8-11
We had a pit roof that was discovered to be in bad shape, following which no one was allowed to
walk on it. This was in effect for over a year until the roof was replaced during a turnaround.
We also had another pit roof that was condemned upon inspection of the pit during a turnaround.
The roof had to be replaced, which added to the turnaround work scope.

7) 12-9-11
Structural Preservation Systems is currently evaluating the roof of one pit using ground penetrating
radar to help define work scope in preparation for turnaround. The technique can reveal loss of
concrete or laminations. It takes about a day to complete the survey then about two weeks to
crunch the data. End result is a map of the roof noting areas of compromised integrity. I was
impressed with their expertise using this technology.

8) 12-9-11
I have noticed that, while not universal, it is fairly common practice to NOT allow traffic over
the pit roof. No direct experience with failure placing personnel in danger.

9) 12-10-11
So, my conclusion from an earlier response is to see if Structural Preservation would like to
expand the use of their radar detection technology to search for tunnels under the US/Mexico
border, to locate drug smugglers...and elsewhere, to look for terrorists!

10) 12-11-11
We've had a refinery rope off a pit roof for about a year until the next turnaround due to
integrity concerns, but don't have a blanket policy preventing roof foot traffic.

11) 12-12-11
We only have one plant with a concrete pit lid and after 40 years it is still in good shape.
Walking is allowed on the concrete lid and no one seems concerned about it. At the other
facilities, we have aluminum pit lids and there is no walking on these lids – they have
grating / catwalks for access to the rundowns, pumps and such.

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12) 12-16-11
We have not had any failures of pit roofs. We have seen superficial cracks and have laid
large sections of aluminum grating (simply to distribute weight out) over these pits.
When Pritchard designed one of our units in the mid 90s, they insisted on a cat-walk above
the pit roof based on their claim that a roof had collapsed and someone had fallen into the pit.

SRU-232 Qatar Refractory Dryout Incident

A few years back, some sulfur recovery units at the big gas processing facilities in Qatar
were being started up. There was an incident where a temporary heater being used to dry
out refractory exploded and killed someone. Does anyone have an industry bulletin or report
concerning that incident?

3-12-12

RESPONSES

1) 3-13-12
There is a brief discussion on the following Qatar Gas web site. It would appear that enough
gas flowed into the vessel to create an explosive mixture before they tried to ignite it.
http://www.qatargas.com.qa/SafetyAlert.aspx?id=207594

SRU-233 Burner Management Standards

• Is there a particular standard that you are aware of that SRU burner management systems
must be constructed to?

4-19-12

RESPONSES

1) 4-20-12
In my experience, the BMS is established by the client setting the requirements with the
detailed engineering company.

2) 4-23-12
Agree, NFPA (for process heaters/boilers) is hard to use as a guide as it doesn't really apply
to the Claus Furnace.

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3) 4-23-12
We have to follow Canadian standard "CSA B149.3 – Code for Fuel Approval of Fuel
Related Components on Appliances and Equipment" but of course this is more applicable to
conventional firing. To vary from this code in Alberta we need a Municipal Variance (local
jurisdiction approval) and have it designed and stamped by a Professional Engineer.
So, at the end of the day, we are using the CSA B149.3 as a 'guide' and fully documenting
where and why we need to take exception.

4) 4-24-12
My experience has been much like others. There is no "officially recognized" standard in
the U.S., but a lot of people fall back to some of the fundamentals in the NFPA which, as
most of us are aware, does not really address the issues we face in our facilities. I suppose
you always have to watch out for local jurisdictional requirements, but unless you shake
some trees you might not ever know and you could stir up quite a storm.

5) 4-24-12
From one of our engineering standards: "Design and selection of the type of BMS system
is typically based on requirements set by ANSI/ISA 84.00.01-2004 Parts 1-3 Safety
Instrumented Functions (SIF) in BMS." These designs range from simple relay systems
to field PLCs to the DCS.

TGT

TGT-057 Quench Column Filtration & Cooling

• Can I get a show of hands from those without sidestream quench water filtration?
• Is anyone using plate exchangers for quench water cooling? Gasketed or welded (e.g.
Compabloc)?

10-6-11

RESPONSES

1) 10-6-11
Have some with filters and some that have bypassed them completely. No plate exchangers.

2) 10-6-11
We have sidestream filtration on most of our units and recommend it for all new ones.
Never will I agree to use plate exchangers in this service due to the fouling issues and
struggles to clean them.

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3) 10-6-11
We have three Stretford Contact Condensers without filters. Our new SCOT has 10%
sidestream filtration. But the SS circulation loop is so clean that the filter only catches trash
and the occasional sulfur glob. I push for Compabloc for most exchanger applications,
but we only have shell/tube and airfans in quench water cooling service.

4) 10-6-11
We have sidestream filtration on most of our units. We do not use plate exchangers in this service.

5) 10-6-11
Most of our TGUs have quench filtration at ~10%, with exception of one Flexsorb TGU
that has none. No plate exchangers in quench service.

6) 10-6-11
I have not seen a unit without filtration. Back in my BP days, one unit had plate exchangers.
They didn't like them and may have switched them out. Another refinery was building a new
unit and during our tour of existing units they fell in love with Compabloc. It was at a tiny
unit in the northwest and the operators loved it. Unfortunately I faded out before installation.

7) 10-7-11
All our units have 10-20% sidestream filtration. One unit is using gasketed plate/frame trim
coolers that require frequent backflushing. Other units use shell/tube, but the newest SCOT
unit will have Compabloc in this service.

8) 10-13-11
Most of our newer US SCOTs are using full-flow filtration on the quench water circulation
loop. If confident of no SO2 breakthroughs, then less filtration should be fine. Allowing
sulfur to form in the quench water and line carbon steel surfaces can result in under-deposit
corrosion that leads to hydrogen blistering.

9) 12-16-11
All five of our quench systems have filtration – four full flow and one at 33%. Cooling is
either by shell/tube or airfans.

TGT-058 Supplemental H2 Quality

We are taking advantage of low-temperature hydrogenation catalyst to replace an RGG with
HP steam reheat, thus requiring supplemental H2. The H2 stream is from a platformer and
at best contains 75% H2 with the other reformer cats/dogs.

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• What problems should we expect from the hydrocarbons, either in the catalyst or amine?

I would think the heavy ends could accumulate in the amine and cause foaming eventually.

12-11-11

RESPONSES

1) 12-11-11
Low-quality reformer H2 contains two very bad actors – chlorides and hydrocarbons.
Chlorides will irreversibly damage the catalyst, and the HCs may crack and/or plug the pores.
The amine problems will come later, not the least of which will be buildup of heat-stable
thiosulfate when the catalyst begins slipping SO2. Ugh !! We have had pooped-out catalyst
that chronically slipped SO2, small enough to not noticeably impact quench water pH, but
enough to produce a slow, steady rise in HSS.

2) 12-11-11
I agree. Steve Massey (Criterion) was dead set against reformer H2 due to likely coking of
the catalyst. In my experience, with three Claus stages you can generally adjust the air
demand set point to maintain 2% H2 at the TGU without supplemental H2.

3) 12-11-11
I agree – should have enough H2 in the tail gas so that supplemental H2 is not required.
Not sure if it is a matter of adjusting air demand as much as keeping the front zone hot
(which is typically done in a refinery to destroy NH3). Dissociation produces H2 and it
does not all disappear on cooling.

4) 12-11-11
I think that most of the problems have been mentioned. In the plant that I know about, the
biggest problems were from the hydrocarbons in the amine, particularly aromatics conducive
to foaming and emulsions. If you are close to SRU/TGU capacity limits you may not be able
to go high on the tail gas ratio, otherwise that is a good choice to avoid the need for
supplemental H2.

5) 12-12-11
Here's another problem: this refinery does not have natural gas or reasonably constant fuel
gas quality, so is using this same reformer gas as fuel to the RGG. Over the past few years,
they have sooted the hydrogenation reactor so often and so bad that they start up the recycle
eductor and eventually pull a vacuum downstream of the reactor. This results in air being

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sucked in, fouling the system with sulfur and contaminating the amine. Without a consistent
source of fuel gas, which option do you recommend?

6) 12-12-11
If you are asking how to better operate the RGG until decommissioned – make sure SRU is on
ratio and adjust RGG air/gas to maintain 2% H2. Is burning propane an option?

I'm confused. Are they somehow using the recycle eductor as a booster blower? Booster
blowers routinely operate with negative suction pressure.

7) 12-12-11
This is a Comprimo design with an eductor after the quench column. They start the eductor
to help with plant hydraulics when the SCOT reactor ΔP becomes high. They can get more
feed in the SRUs with the eductor online but they also start to pull a vacuum downstream of
the reactor. This is where they have found leaks that allow air to be pulled into the process.

8) 12-13-11
We are using SMR H2 in our new LT SCOT and expect only intermittent use during upset
conditions as there should normally be sufficient H2 in the tail gas as previously mentioned.
There is concern even with SMR H2 of lube oil carryover and have made provision for a
future filter if this is an issue. As an aside one of our plants currently has so much H2 in
the tail gas that it is interfering with stack O2 measurement.

Regarding the reformer H2 contaminants, it seems you are just transferring the problem from
a burner fuel issue to the direct H2 injection and, although this may be an intermittent feed,
the contaminants will still deactivate/plug the catalyst and reduce the run length. To improve
the reliability of the unit the Reformer H2 needs to be cleaned up with a chloride removal
bed and additional purification to remove the hydrocarbons.

9) 12-13-11
We use reformer H2 in four of the five refineries with TGUs. In two of these plants, the
reformer H2 is also used as the fuel source to the feed heater burner. We rarely have issues
with sooting. However, H2 purity is typically > 90%, possibly because the reformers are CCRs.
In addition, all the H2 goes through chloride guard beds. Years ago, when there was a
reformer catalyst issue at one of the refineries and H2 purity dropped into the 70% range,
the tail gas reactor bed was sooting up every couple of months until the reformer
catalyst was changed out.

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10) 12-16-11
Agree with others’ comments. We have two units currently on reformer H2, and are installing
purchased H2 capability for the reasons mentioned.

11) 12-16-11
Within the last three months we have commissioned two new units with steam preheat (both
saturated/superheated) and using reformer H2. So far, the catalyst is operating at 480°F inlet
and no signs of hydrocarbon fouling/deactivation. Another of our plants has run this way
since 2003 without incident, but not with LT catalyst. They had a choice of two H2 sources.
One gave them some heavy liquid, but it did not do anything beyond accumulating in the
preheater and increasing pressure drop. We drained the liquid and switched to the other
source and have since been free of problems. In most other plants we tend to specify PSA
hydrogen first before going to less pure sources.

12) 12-19-11
I have seen problems as mentioned with liquid HCs in reformer H2 causing soot problems
over the 3-5 year catalyst life. These units benefited from installation of efficient KO drums
on the H2 stream, located close to the TGU reactor.

TGT-060 RGG Cooler Corrosion

Since last turnaround we have seen a significant increase in process-side pitting on the lower
portions of the carbon steel tubes in our SCOT RGG Waste Heat Boiler (before the
Hydrogenation Reactor). Steam pressure is 380 psig. Recent changes include a sweeter
crude slate and new SRU – both resulting in high turndown forcing us to recycle tail gas
using the startup blower to moderate RGG outlet temperature.

• Has anyone has a similar experience?

3-6-12

RESPONSES

1) 3-6-12
Has the process exit temperature decreased significantly with the change?

2) 3-6-12
More questions than answers:
• What is RGG fuel, air/gas and steam/gas?
• Is startup blower suction negative?
• Does startup blower have tandem shaft seals with N2 pressure?
• Is burner high intensity?

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3) 3-7-12
What is your BFW temperature and where does it enter the heat exchanger? I had experience
with an SRU/TGU operating at high turndown with BFW entering the bottom of the exchanger
at generally < 250°F, and sometimes closer to 200°F. The sulfur condenser bottom tube rows
plugged with solid sulfur, compounded by under-deposit corrosion, and the TGU Reactor
Effluent Cooler bottom row also corroded rather quickly.

4) 3-7-12
Pitting is typical of under-deposit corrosion. If burner is low intensity, are you occasionally
making soot at high turndown?

Cold recycle gas is typically combined with SRU tail gas upstream of the RGG, likely resulting
in a noticeable buildup of solid sulfur over a few days. If operators periodically stop recycling
to melt the sulfur to alleviate pressure drop, entrained droplets combined with soot
simultaneously generated due to high turndown could conceivably coalesce as a viscous coating
on the tube wall and gravitate to the bottom.

Since the heated tail gas is unsaturated, the liquid sulfur may tend to weather off, leaving a
porous, highly carbonaceous matrix containing interstitial H2O and SO2. I presume tube
skin temperatures are too high for even capillary condensation at operating temperature, but
sulfurous acid would promptly condense when the unit is idle.

5) 3-7-12
I do not know the corrosion mechanism. However, I have also seen corrosion on the bottom
row(s) of tubes in the cooler. One plant was able to find a design to change from carbon steel
to an alloy to avoid the corrosion. I don't remember how they did it but I do remember that
there were major concerns about using alloy in fixed-tubesheet exchangers. It was not easy
but they did find a solution.

6) 3-7-12
We haven't seen problems in this area.

7) 3-7-12
All our SCOT boilers generate 50 psig steam and are downstream of the Reactor; no
corrosion issues. Have only seen one third party application such as yours, and do not have
significant experience to comment on the corrosion you are observing.

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8) 3-8-12
All of our TGU boilers also generate 50 psig steam, and we have not seen any corrosion
issues, even at high turndown.

9) 3-11-12
Before a recent comment, I did not realize the WHB is before the Reactor, which I have
not seen before. That changes the chemistry – the porous carbonaceous deposits now contain
interstitial H2O and SO2 which will promptly condense as sulfurous acid when the unit is
down (as my previous response is revised).

10) 3-12-12
I also did not catch the "before" aspect. We did have significant trouble when incinerating
an elemental-sulfur containing gas in front of an SO2 absorption style TGU. The WHB was
destroyed by sulfuric acid – I watched as the chrome solution dripped from the exit pipe!
DuPont cautioned us that SO3 formation was common in elemental sulfur burning.

SWS

SWS-031 Tray Efficiency & Packing HETP

• What are typical tray efficiencies and packing HETPs in sour water strippers?

My recollection from a former life (and very dated, unfortunately) are that there were
considerable variations.

8-26-11

RESPONSES

1) 8-26-11
For new construction, we tend to use a 50% Murphree tray efficiency or 33% overall
efficiency
for sour water service. Model it both ways and use the most conservative.

2) 8-26-11
33% efficiency has been our standard value. 10 feet of packing is equivalent to about 3 trays.

3) 8-30-11
Our current strippers have 36 trays in the stripping section and were simulated using 12

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theoretical trays or 33% efficiency.

4) 8-31-11
It probably has more to do with which property package (EOS) you are using in this primarily
water based system. I am still betting that about 4 feet of random packing will get you a
single theoretical stage or just go with 33% on the efficiency for a tray. Structured packing
may be a bit different.

SWS-032 SWS Bottoms Fouling with Elemental Sulphur

At one of our refineries we have an ongoing fouling issue in the SWS that we have not seen in
our other stripper units. The deposit material is fouling the SWS bottoms stripped water side
from the feed-bottoms heat exchanger, outlet piping and pump. Operations are having difficulty
controlling the SWS level due to fouling in the control valve. See attached analytical reports for
a recent sample. The deposits are mainly elemental sulfur accounting for 95+wt% of elemental
sulphur in a 2007 sample, but more recent 2012 samples contained 70% S and 30% carbon and
this material can not be melted so steaming out the SWS is no longer an option for removal.
Frequency of the fouling is every 1-2 years and seems to happen fairly quickly when it occurs.
Questions:

1. Any experience or knowledge related to carsul formation in the bottom of SWS?

2. What causes element sulfur contamination in sour water? One theory is oxygen ingress
into the sour water system resulting in direct oxidation of H2S to sulfur which becomes
insoluble in the SSW.
3. What about sulfiding agent use in hydrotreating catalysts, could they play a role in
sulphur contamination in sour water?

7/11/2012

RESPONSES
1. 7/16/2012: NOTE: the sour water tank has a floating roof vented to atmosphere with a
diesel blanket layer.

2. 7/16/2012: Re quench water SO2 as an oxidant source, there is no SCOT unit at this
refinery.

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3. 7/16/2012: Sorry, don't have any of these to worry about (lucky me).

4. 7/12/2012:
We have seen similar fouling in the sour water loop of flare gas recovery systems. Most of
our FGR systems use liquid ring compressors and generate a small sour water purge
stream. There are strainers on the circulating water going back to the LRCs and we have
experienced rapid strainer fouling with sulfur/FeS. We have correlated degree of fouling
with oxygen in the feed gas. Vacuum unit off-gas, a notorious culprit for O2 ingress, is
commonly the root of the problem. We are managing the issue by using dual strainers with
spare SS baskets for quick changeout. Strainers are sometimes swapped 3-4 times daily. In
your case, the SWS may be seeing a water stream that has dissolved O2 that when mixed
with H2S in solution eventually yields sulfur particles and all of its associated challenges.

5. 7/12/2012: At risk of stating the obvious, O2 in some form is the culprit. As I see it,
elemental sulfur in the sour water exists as a combination of colloidal sulfur and
polysulfides. Once temperatures exceed 120 C in the lower stripper, colloidal particles
coalesce into microscopic globules of liquid sulfur upon which organics tend to glom,
subsequently depositing as an organosulfur matrix at < 120 C. Also, my understanding is
that elemental sulfur can be an oxidizer in aqueous systems, and my experience suggests
that polysulfides thus also tend to promote tray fouling with polymerized organics. (See
SWS-002.)

6. 7/16/2012: I asked my partner to wade in on this since we recently encountered a similar

situation in Oman. His comments --

1. Any experience or knowledge related to carsul formation in the bottom of SWS?

Looks like they are getting some heavy hydrocarbon in the sour water system.

1. What causes element sulfur contamination in sour water? One theory is oxygen
ingress into the sour water system resulting in direct oxidation of H2S to sulfur
which becomes insoluble in the SSW.

Could be O2. They did not mention SCOT Unit quench tower as source of SO2.

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 2. What about sulfiding agent use in hydrotreating catalysts, could they play a role in
sulphur contamination in sour water?

My understanding is sulfiding agents breakdown to H2S so I would not expect that

as a source of elemental sulfur in SWS.

7. 7/11/2012: I don't recall ever seeing elemental sulphur in the SWS as you described.

However, we did have a lot of deposits which we attributed to the coke fines. We used to
have to shutdown and chemical clean every 6-months. We are now back to a more typical
2-years.

8. 7/11/2012: Nothing new to add. Agree that O2 somehow is the culprit

9. 7/11/2012: Are sour water storage tanks floating roof, inert gas blanket or vented to
atmosphere with diesel/kerosene layer?

10. 7/11/2012: We have seen repeated SWS fouling more typically from hard water deposits.
We did have a SWS totally plug up when polysulfide injection was left running when the
column was shut down. Since the Claus reaction can occur "everywhere," would seem to
me, at least, that O2 intrusion could be reacting with the abundant H2S to form SO2, that
then further reacts to sulfur. Will leave the more precise interpretation of the data you have
presented to Messrs Keller and Hatcher, et al.

GEN

GEN-035 Decommissioning Odorant Tank

• What procedures are being used to decommission odorant tanks?

I notice that there is an outfit (MRR) that will seal up the tank haul it away and use a
furnace to thermally destroy any remaining odorant.

• Are there methods to chemically clean onsite, and reuse the tank for another purpose.
• For example, has anyone tried Merox (caustic plus catalyst) to convert all the
remaining mercaptan to disulfide oil?

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12-9-11

RESPONSES

1) 12-9-11
I thought the practice was to flush with diesel.

2) 12-12-11
I believe the best way to eliminate the stink is by filling it with Chlorox and then dumping that to waste. Not

3) 12-12-11
If you do an internet search of mercaptan neutralization and/or mercaptan deoderant, there are several compa

4) 12-12-11
Peroxide or KMnO4 may be useful here. Chemical cleaners should be able to recommend one. I have no dir

5) 12-14-11
Our cleaning expert recommends inhibited acid wash, followed perhaps by some neutralizing wash such as d

6) 12-14-11
No experience with decommissioning, but some time ago we discussed the metallurgy needed in systems wit
7) 12-15-11
Have fun considering the product noted for use in neutralizing mercaptans in humans and produced from an o
http://www.champex.co.uk/tech1.asp

I also ran across another article that discussed attacking mouth odors (including mercaptans) with toothpaste.
mild since it would be exothermic.

Of course, I'm not sure how the mercaptan additive carrier solvent that remains in the vessel would respond t
to oxidizing agents.

8) 12-19-11
If the tank is located in a refinery, I'd flush the contents with kerosene/diesel and then send the mixture to a h

I "know" of an incident many years ago where the operating persons "thought" an abandoned odorant tank ha
complaints since the stench drifted into a neighborhood and school about ½ mile away.

[ ABPG Presentation – LHS – Brimstone Sulfur Symposium at Vail 2012.doc ] LHS/08-20-12

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