Air and Gas Drilling Manual

1998 TOC
1998 Q&A
V. Energy & Environmental Management
A. Sulfur Recovery
Amine Plants
Question 1.
What is the most economical method to remove heat stable salts from a large
amine unit running either EA or MDEA? Do oxygen scavengers prevent the
accumulation of heat stable salts?
MASTRACCI:
We found ion exchange be the most economical way to remove heat stable salts from a
large amine circulation system. We have had success using two commercially available systems
to reduce heat stable salt concentrations. In the case of our Eagle Point Refinery in New Jersey,
this has significantly reduced corrosion in FCC amine absorber and associated equipment.
We have not used oxygen scavengers at our refineries since they appear to only reduce the
rate of formation and not eliminate heat stable salts form the system.
ZETLMEISL:
The two methods I am familiar with are vacuum distillation and ion exchange. Vacuum
distillation is preferred when the contaminants are a combination of heat stable salts and amine
degradation products or heavy oils, as ion exchange will remove only the heat stable salts. When
using vacuum distillation, sometimes caustic is added to bring about a sharper dissociation of the
amine from the heat stabile salts. Major costs come from energy, unrecoverable amine in the
reclaimer waste, waste disposal of the bottoms, and caustic when it is used.
Ion exchange is a very effective way to remove heat stable salts from any amine solution.
Caustic is used to regenerate the ion exchange beds followed by water wash. Major costs from
ion exchange reclaiming are: caustic, clean water, waste disposal of the dilute caustic
regeneration stream and resin replacement.
Economic differences between these two methods of reclaiming amine depend on the way
water vs. energy is valued at your location and how waste is managed.
There is a little bit of controversy on the question of oxygen scavengers. We find that in
some cases they may mitigate the formation of carboxylic acid and oxidation products of the
amines. But they cannot possibly eliminate all heat stable salts, only those that are going to be
formed from those oxidation products. In most cases, the larger portion of the heat stabile salts
are from the other strong acids that occur in the acid gas stream. Formation of these heat stable
salts is not going to be touched by oxygen scavengers.
SMITH:
This question was basically answered in 1995 by Mr. Dale Hansen of Valero and others.
(Session #1, section A, subpart 1 (Amine Plants), question #2). I will read a brief excerpt from
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that discussion. “At Valero, there are three amine systems, two primary systems and one tail gas
system, (all using MDEA). The primary amine system associated with the hydrotreating units
has not experienced heat stable salt build up. The primary system associated with the heavy oil
cracker has experienced heat stabile salt buildup and pluggage of the fuel gas absorber, when
heat stabile salts reached about 3 percent.
We have successfully used an amine formulation, which does not allow buildup of heat
stable salts. The tail gas unit amine system experienced heat stable salt buildup which caused
pluggage of an absorber when the level reached several thousands parts per million. In this
system, we successfully modified the amine formulation, instituted use of an inhibitor and made
changes in the reactor system to reduce the introduction of acid components. The heat stable salts
buildup problem we experienced began when we were successful in reducing system amine
losses”.
I will add that the formulated MDEA solvent that we use is MDEA HST and it has
controlled the heat stable salts. We have been using it for the last four years.
TRAEGER:
I agree with most of what has been said. Determination of the most economical option
will depend strongly on the individual refiner's situation.
I have a list of some important items that would have to be considered. Many of them
were brought up, but they would have to be considered for each application to determine which
one was most economical. These include the frequency of the cleaning and the level of the
incursion rate.
Secondly, other methods besides online treatment should be considered as well as the
types and quantities of waste generated. The overall amine recovery rate and additional
chemicals are required for the removal process must also be considered. Finally, there is the
level of support required by the refiner to aid in the completion of the process.
One rough cost estimate I can provide is that for an electrodialysis method, the overall
reclamation costs are estimated to be 25-50% of the value of the amine that is treated.
MASTRACCI:
We found that ion exchange is the most economical way for us to remove heat stable
salts from large amine circulation systems. We have had success using two commercially
available systems and in the case of our Eagle Point refinery, we were able to significantly get the
corrosion rate in the FCC amine absorber and associated equipment well under control.
Regarding the use of oxygen scavengers, they appear to only reduce the rate of formation
and not eliminate the heat stable salts. Therefore, we have not used them.
ROBERT L. HORAN (MPR Services, Inc.):

We have documented the savings and increased profitability to refiners associated with
maintaining low levels of heat stable salts in their amine solutions. Our experience shows that
ion exchange is the most economical method for removing heat stable salts. This is because the
ion exchange process selectively removes only the impurities in the amine solutions. Also, it
does not require the addition of extra chemicals.
JOHN SORIA (Hci Coastal Chemical, Houston, Texas):
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The existence of corrosive species other than heat stable salts (HSS) is often overlooked
with costly consequences. For instance, DEA and MEA react with CO2 to form other type of
degradation products. These products, such as HEED, THEED, BHEP, HEOD, etc., are non-
ionic and thus they cannot be removed by ion exchange. These impurities increase corrosion
potential in two ways. First, by being excellent chelating agents they remove/destroy metallic
films protecting carbon steel as well as stainless steel equipment and piping. Second, THEED for
instance, is a diamine that has two nitrogen sites. One nitrogen site is more basic than the original
DEA. This results in the formation of a very strong bond with CO2 making it difficult to achieve
a low CO2 loading in the lean amine. As the THEED concentration increases, more and more
CO2 remains in the lean amine leaving the reboiler. Some of the CO2 is then stripped in high
heat-flux areas of the reboiler or it is released in areas where velocity changes occur such as
control valves and pumps. The resulting corrosion is in the form of localized pitting attack on
carbon steel. This often leads to premature equipment and piping failures. The attack on stainless
steel components is generalized and results in high levels of chromium in solution thus causing
the solvent to turn blue. In addition to increasing corrosion potential, non-ionic degradation
products increase foaming tendency and increase fouling potential. Non-ionic degradation
products can only be removed via distillation.
Hci Coastal Chemical manufacturers and markets patented corrosion and fouling
inhibitors that overcome the effects of both heat stable salts and as non-ionic degradation
products. There are currently over 70 amine units using this technology in the USA and Canada.
Several applications will start in the near future in Latin America and the Middle East. This
technology is also used in aromatic extraction units (Sulfolane, TETRA, UDEX), glycol
dehydration units, sour water strippers, and quench towers.
TOM BACON (DOW Chemical Company):

Heat stable amine salts (HSAS) are formed with acidic compounds as they enter or are
formed in the amine system. Typical acids in the inlet gas or liquid include hydrochloric (HCL),
Sulfurous (H2SO3), and hydrogen cyanide (HCN). These form salts directly with whatever base
they encounter.
Typical HSAS precursors entering the amine system include oxygen (O2), carbon
monoxide (CO), sulfur dioxide (SO2), and HCN. These react in the amine solution and form
byproducts that form HSAS. O2 causes oxidative degradation of any amine. The resulting
byproducts can include formate, acetate, glycolate, and oxalate. CO reacts in an alkaline
environment to form formate. CN reacts in an alkaline environment to form formate and with
sulfur or SO2 to form thiocyanate (SCN). SO2 reacts with polysulfide to form thiosulfate (S2O3).
H2SO3 oxidizes to form sulfuric (H2SO4).
Treatment with an oxygen scavenger could reduce salts formed by oxidation, however
these are not necessarily the principle source of HSAS. Water washing the inlet gas prior to
entering the amine contactor could reduce water soluble HSAS precursors, but not O2 or CO.
Proper management of FCC and Coker gas water or polysulfide injection can reduce CN.
DAVID BURNS (Union Carbide Corporation):

In considering this question the scope really needs to be broadened to address how you
“manage” heat stable salts most economically. While removing them is certainly a part of the
consideration, in many instances heat salts can be managed in such a way that control, rather than
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removal, is sufficient. In this regard a proper heat stable salt management program should include
mitigation (e.g., feed-gas water washing), monitoring (e.g., analytical), control (e.g.,
neutralization), and finally removal. As has been discussed many times at the Q&A Sessions over
the years, neutralization is a very effective way of controlling heat stable salt problems and many
testimonials have been given outlining its benefits. However, if the accumulation rate of heat
stable salts is too great, a point may be reached whereby some form of removal is required. There
are several commercial on-line processes currently available using either, electrodialysis, ion-
exchange or vacuum reclaiming technology (and these have been reviewed in the most recent
addition of Kohl & Reisenfeld, 5th ed, pp 242-269, Gulf Publishing (1997)). Dedicated on site
reclamation units utilizing these technologies can be purchased or leased but mobile processes
are also available that can be used on a fee-for-service basis. For most refinery situations it
usually proves most economical to use the mobile services (and is always preferable to off site
reclaiming). In deciding upon the most economical reclamation process in addition to the
underlying service fee, consideration should to be given to the recommended frequency of
reclamation, the type and volume of effluent generated by the process - whether it is aqueous or
organic, solid or liquid, the quantity of ancillary chemicals required in the process, the overall
amine recovery, and the degree of on site support required to support the service provider and
their operation.
Union Carbide’s experience with electrodialysis indicates that the overall reclamation
cost is typically 25-50 % of the replacement value of the amine. It produces an aqueous brine
effluent and generally results in a 98% recovery of the amine.
Our experience is that oxygen scavengers do not prevent the accumulation of heat stable
salts since, for the most part, oxidation of the underlying amine or other gas constituents is not
responsible for heat stable salts in the first place. Heat stable salts mainly result from the
incursion of the acids themselves, or their precursors, into the amine unit. Thus the incursion of
gas contaminants such formic acid, CO, HCN, HCL, or acetonitrile can lead to chloride, formate,
acetate, or thiocyanate amine salts (to name a few) without the amine itself degrading. Amines
can degrade oxidatively to various carboxylic acids but they tend to be more stable to oxidation
than is generally thought and require more aggressive conditions than are generally seen (e.g.,
high temps and O2 partial pressures). At the O2 levels required to generate appreciable heat
stable salts significant quantities of oxygen scavengers would be consumed - and there is always
the concern of what the resulting product of this would be and what its impact on the amine
system itself is.
Question 2.
What are the causes for losses in amine treaters, and what are the typical
amine losses? How much of these losses are from solubility, and how much
from entrainment? What technology is available for minimizing the
carryover?
RADCLIFFE:
I have 14 years of refining experience with Amoco Milford Haven, which became Elf
Milford Haven, and the primary cause of loss that we had was entrainment due to foaming. The
foaming itself was due to light cycle oil contamination. The light cycle oil came from the
secondary absorber on the FCCU. We solved the problem by putting in a carbon filter, which
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treated a 10 percent slipstream of the circulating amine.

Other causes of loss include leakages as have already been mentioned and blow down
where that is used to remove heat stable salts. If you do get an upset, one thing you might want to
consider where you have a high buildup of heat stable salts, is to do off site regeneration which
saves a lot of money in buying new amine. That has being done successfully by a company called
PCK in Germany.
In terms of the design of carbon filters, there is a paper called "Redesigning Filters Solve
Foaming Amine Loss Problems at a Louisiana Gas Plant" by Pauley, Langston and Betts. It is in
the February 4, 1991 Oil & Gas Journal.
Another recommended tip to avoid foaming due to heavy hydrocarbon condensation in
the absorber is to keep the H2S rich stream to be treated in the absorber at least 5ºC or 10ºF
cooler than the amine stream.
SMITH:
There is an excellent article on amine losses in the May 1994 issue of Hydrocarbon
Processing entitled "Reduce Amine Plant Solvent Losses" by E.J. Stewart and R.A. Lanning.
They identified and quantified losses as mechanical, entrainment, vaporization, degradation and
solubility.
Our engineering department at Valero reported that we see normal losses of 50% due to
solubility and 50% due to entrainment. They also stated that three general equipment topics have
been investigated at Valero. These are proper sizing of the equipment, mist eliminators and
adequate cooling.
After talking to the operations department, they reported 90% of our amine losses are due
to skimming the flash drums, when drawing hydrocarbons. Typical losses are from 2-3,000
pounds a month.
ROBERT ALLEN LANNING (KTI Fish):

A systematic approach to reducing amine plant solvent losses begins by measuring
current loss rates and ranking them according to loss category. The five areas of losses are:
vaporization, solubility, degradation, entrainment, and mechanical. In refinery amine systems the
loss rate may vary greatly from plant to plant. In general, the highest loss rates are usually
associated with mechanical and entrainment losses. Plants with liquid treaters can incur high
losses due to entrainment and solubility of amine in the LPG stream. Targeting the high loss
categories with improved operating procedures and engineering design practices can result in
cost savings and better plant operation.
For more information on how to identify and solve these problems I refer
you to an article that I co-authored titled "Reduce Amine Plant Solvent Losses". The article
appeared in the May and June 1994 issues of Hydrocarbon Processing.
ARTHUR W. DEZEEUW (Koch-Glitsch Field Service):

Our experience has been that amine losses are highest due to entrainment or carryover,
both from LPG absorbers (liquid/liquid) as well as from contactors (gas/liquid).
In the case of the LPG contactors, a proprietary mesh type coalescer pad design is
available to fit into the top of the contactor This is the best way to contain entrainment losses.
In the case of gas contactors, a proprietary Demister high efficiency mesh pad in the top
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of the contactor can reduce these losses by an order of magnitude.

In addition to these improvements, replacement of the skimming device in the rich amine
drum with a proprietary coalescing element will eliminate amine losses.
These improvements have been demonstrated in more than 100 installations.
JOHN DIBBLE (Aminetech, Inc.):

Causes of amine losses include vapor losses, contamination with hydrocarbons, heat
stable salts and ion sulfide. Improper process conditions also contribute to the losses. Most losses
occur as entrainment. MDEA LF when used with optimized process conditions averages less
than one inventory loss per year.
MODESTO ORTIZ (MPR Services, Inc.):

MPR's experience is that the largest losses in amine treaters are caused by corrosion
products and hydrocarbons. We have seen that maintenance of low levels of iron sulfide,
hydrocarbon and heat stable salts is critical in minimizing losses. For example, a refiner was
loosing solvent equal to approximately three system volumes per year of MDEA. Through the
use of a heat stable salt management program based on MPR’s HSSX Kidney and an
aggressive attack on the source of losses, this refinery had a 90% reduction in losses. For
additional information please refer to an article authored by A. L. Cummings & S.M. Mecum
titled "Remove heat stable salts for better amine plant performance". The article appeared in the
August, 1998 issue of Hydrocarbon Processing. MPR offers a slip stream technology to remove
all three of these factors which are iron sulfide, hydrocarbons, and heat stable salts. The
technology is available as a mobile process and also as a permanent installation.
JAMES LEWIS (TPA, Inc.):

I believe everyone has adequately described the source of amine losses, and I would like
to provide some quantitative information.
Solubility: Values can range from 0.02 to 0.10 pounds of amine per barrel of LPG
treated, and will vary with the type of amine, amine solution strength, and the temperature of the
two streams (LPG and amine stream). Solubility losses can be minimized by the use of a water
wash loop.
Entrainment: Typical values are 0.8 to 8.0 pounds of amine per million standard cubic
feet a day of gas, and will vary with equipment configurations and operations.
Overall system losses for a well designed, well maintained, well operated facility can be
as low as one system inventory per year. However, losses can be substantially higher and will
vary with the type of amine, amine solution strength, temperature of the amine, temperature of
the sour stream, system throughput, system cleanliness, and unit operations.
PATRICIA FORERO (Merichem Company):

Amine losses from amine treaters result from amine solubility in the stream being treated
and from amine entrainment with the stream being treated. Solubility varies depending on the
type of hydrocarbon. Entrainment varies depending on the type of mixing employed. Amine
extraction towers have considerable carryover when flow rates are above design, constant
pressure swings occur, and when corrosion fines build up in the circulating amine causing
emulsion tendencies.
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Generally speaking, solubility is about 200 wt ppm when you are using MDEA for
example, and entrainment can be as much as 1000 wt ppm.
The Fiber Film™, AminexΚtechnology system reduces the amine entrainment to no more
than 5.0 wt ppm. Water washing the amine treating product in a Fiber Film™,
AquafiningΚsystem with a continuous addition and withdrawal of water will allow the refiner to
recover most of the soluble and insoluble (entrained amine) by sending the effluent water to the
amine regenerator.
The removal of amine via water washing the hydrocarbon ahead of the caustic treating
gives the added advantages of caustic savings (amine dilutes the caustic and the H2S in the amine
consumes the caustic) and minimizing the quantity of amine in the refinery effluent, which has
environmental implications.
A caustic treating system will not remove amine from the hydrocarbon like water washing
does because the caustic is not dumped often enough. Thus, the amine remaining in the caustic
treated product can be troublesome for downstream fractionators in meeting product
specifications.
JAMES JENKINS (Huntsman Corporation):

The amine best practices group conducted a good survey for amine losses. As a followup,
we tried to do our own informal survey. What we are finding is in the combined treating systems
that loss rates really were not amine type specific. The other thing that we have noted is that
typically the plants that were running at average or above average actually seemed to be the
plants that are more complex in that they have a higher number of contactors and they were very
remote from the sulfur complex. So when you are evaluating your plant you also need to look at
your complexity and the amount of liquid treating.

Amine losses can occur as a result of physical and chemical situations. Chemical
losses occur as vaporization in treated or acid gases, solubility in liquid hydrocarbons, or
reactions forming heat stable salts or degradation products. MEA is the only typical amine
that has appreciable vaporization losses. MDEA has a higher solubility in liquid hydrocarbons.
All amines will form heat stable salts. All will degrade, but the rates differ. Reclaiming to
recover amine from heat stable salts will recover only a portion of the bound amine.
Physical losses occur as liquid entrainment in gases, liquid emulsion or entrainment in
liquid hydrocarbons, drainage for maintenance on equipment or filter replacement, leaks and
drips, and inadvertent misalignment of process valving.
The actual amine loss rate for a system is typically several times higher than the
theoretical chemical rate. A water wash for MEA gas treaters and any LPG treater will minimize
the chemical losses. Physical losses can be reduced with good, inexpensive attention to
operating discipline.
DUKE TUNNELL (Amine Best Practices Group):

ABPG surveys indicate average amine replacement is about three inventories per year. In
other words, an average amine molecule spends only four months in the unit. The median is
somewhat lower than the average, indicating that there are a few refiners with really bad losses
and the bulk of the industry is below the average. This figure is many times higher than either
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solubility or vapor pressure losses would account for. Volumetric loss rate is independent of type
of amine: almost everybody has high losses. The cost of the losses, of course, varies with the
cost of the amine. MDEA losses tend to be more expensive than MEA or DEA losses.
The only clear cause the surveys identified for losses is the amount of liquid treating a
refiner does. There was a direct correlation between the percent of the lean amine sent to liquid
treaters and the amine loss rate. The surveys also indicated that refines who have water wash
vessels on the LPG out of the amine treaters experienced substantially lower loss rates than the
average by a factor of three.
KENNETH G. TASKER (IFP North America):

I would like to survey the panel on what data are available on the foaming tendency and
therefore loss of amine from carryover due to aromatics pickup, and also to survey the panel on
the ranking of the various amines on their propensity to pick up aromatics. One of the responses
given mentioned LCO contamination as an issue and perhaps Mr. Radcliffe, the panel member
who referenced this, could expand on it a little.
RADCLIFFE:
I do not have any data directly related to your question.
ERIK STEWART (The Dow Chemical Company):

An amine loss paper was presented at the 1991 Gas Conditioning Conference in Norman,
OK. An updated paper was published in the 1994 May and June issues of Hydrocarbon
Processing.

Solvent losses result from vaporization into the treated gas leaving an absorber and the acid
gas leaving a regenerator, solubility in treated LPG and mechanical losses from the system such as
during filter changes or due to seal leaks. Typical refinery losses can range from 30% of the solvent
inventory per year up to 200%, depending on the size and complexity of the system and the care
taken to avoid process upsets. Under normal operating conditions, solubility and vaporization should
account for the majority of losses. A single process upset, however, could produce entrainment
losses far in excess of typical losses. To minimize the carryover of solvent, a knock out drum should
be located downstream of gas absorbers and a water wash loop with coalescer can be used
downstream of LPG treaters.
Question 3.
What creates corrosion in amine overhead systems and what methods can be
used to contain it? What types of corrosion inhibitors may be used to control
corrosion in amine systems?
ZETLMEISL:
The corrosion mechanism is wet acid gas corrosion and is dependent on the concentration
of the various contaminants in the overhead system. The predominant corrosion mechanism is
ammonium bisulfide corrosion due to the buildup of ammonia and H2S in the recirculating reflux
stream. The corrosion is accelerated by the temperature and velocities present in the overhead
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system.
One thing that can be done to mitigate the corrosion is the addition of an overhead
condensate purge or bleed to reduce the concentration of recirculated contaminants, i.e.,
ammonia, cyanide and organic acids, in the overhead system. The purge design should consider a
balance in the reduction of the contaminants and the amine losses.
A second option is the addition of an inhibitor program in the overhead system. The use
of a lean amine slip stream to inject and distribute the inhibitor has an added advantage of adding
small quantities of makeup amine to modify the pH of the wet acid gas condensate.
Finally, general operational control of the amine system will reduce contaminants in the
overhead.
The corrosion inhibitors that are commonly used are either film forming or passivating
types. The film forming inhibitors are usually proprietary organic compounds, e.g. derivatives of
polyamines, designed to provide a protective layer on the metal surface. The passivating types are
compounds that actually react with the metal surface, and modify the surface structure.
Obviously, any inhibitor must be compatible with the amine system and must not cause
undesirable side effects such as foaming.
MASTRACCI:
The corrosion mechanism is typically wet acid attack often at the phase interface or
under-deposit corrosion. Most overhead systems will have small concentrations of hydrogen
sulfide, carbon dioxide and ammonia along with traces of chlorides.
The system pH tends to vary in the range of 6.5-7.5. This is where the metal sulfide
protective film may be affected. The metal can be protected by most amine based inhibitors, or
by injecting a slip stream of lean amine into the overhead system to maintain 2-3% amine in the
water phase.

Corrosion in amine regenerator overhead systems is caused by ammonium bisulfide,
HCN, and erosion. Ammonia absorbed from the inlet gas can accumulate in the reflux loop and
react to form ammonium bisulfide, which is corrosive. HCN can accumulate in a similar
manner, and will inhibit or destroy iron sulfide passivation. Condensation in the regenerator
overhead condenser can erode or wash away passivation in downstream piping.
Systematic purging of a portion of the regenerator reflux minimizes buildup of these
contaminants. In the absence of ammonia, a small amount of amine carryover or vaporization
will buffer the pH in the overhead system.
DUKE TUNNELL (Amine Best Practices Group):

ABPG survey data shows that corrosion in the amine regenerator overhead system is the
most commonly experienced, and is almost always related to excessive ammonia concentration
in the regenerator reflux water. The survey data show this trend, but the data are too sparse to
speak with confidence. The limit on ammonia concentration in the reflux water should be in the
5,000-7,000 ppmw range. Cyanide in the regenerator overhead acts to exacerbate corrosion rates
from ammonia.
JACKSON:
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Corrosion of amine overhead systems can occur in several places in the piping and
associated equipment. Major factors are acid gases present, percent of design operation, and
metallurgy.
Physical entrainment of liquid droplets in the overhead stream can result in erosion of
metal surfaces at points of impact.
Condenser exit nozzles and piping from the condenser to the reflux drum are at risk.
Erosive slug or plug liquid flow can occur if acid gas rates are well below design, which occurs
during startup and shutdown. Placement of corrosion probes or other sensing devices can cause
gross disturbance of the annular liquid flow resulting in accelerated corrosion.
Gross amounts of ammonia and low overhead temperatures can result in the formation of
solids or non-protective iron sulfide films.
If CO2 is the only acid gas present, formation of carbonic acid can occur in condensed
water and this usually requires a metallurgical solution to prevent corrosion.
Rather than using a corrosion inhibitor, a small volume of lean amine can be added to the
overhead system to mitigate corrosion. This reduces the potential for excessive amine foaming
and shortened carbon bed life.
Question 4.
What is the experience in switching from one amine to another amine in gas
and liquid systems? What amine strength was used in each system, and how did
you determine what strength to use?
TURPIN:
Years ago I was involved in switching a gas/MEA system to a gas/Sulfinol system. We
experienced a significant increase in capacity without having to replace the major pieces of
equipment. We did have to add some equipment like a reclaimer and a carbon filter. As I
remember the new piping specifications required that we go back and stress relieve some of the
old piping. The MEA strength was about 20%, the upper limit to maximize the system capacity
but still keep corrosion reasonable. The composition of the DIPA/Sulfinol mix was specified by
the supplier.
We had significant problems during the initial months of operation and blamed the
process supplier, the mechanical contractor and the project engineers – none of whom were
found to be at fault. The process ran fine when we repaired some trays in the absorber that were
damaged during start-up.
Two of the things I learned on that project were not to jump to conclusions, and finger
pointing does not help solve process problems.
SMITH:
Valero used to use DEA but switched to MDEA about ten years ago. Typical strengths
that we use are 25% in our heavy oil cracker system, 40% in our hydrotreating units and 25% in
our sulfur tail gas system.
When switching to another amine to gain capacity, one needs to be aware that higher
strengths are possible with MDEA. This can increase losses in liquid contactors. One must
realize that there is a tradeoff between losses versus capacity in some circumstances. Basically,
we use the lowest possible strength MDEA that we can get away with.
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TRAEGER:
I would agree with Mr. Smith. Our amine system treats both our fuel gas and our liquid
olefin stream from the FCCU. When we converted our amine units from DEA to MDEA, we
provided amine supplier with absorber tower, stripper tower design information as well as well
as analyses of the streams to be treated.
The target concentration was a 40 wt% MDEA. That was determined including
minimizing circulation rates, maintaining acceptable rich amine loadings, acceptable CO2 slip
and considering phase separation in the liquid treater.
Conversion was completed during a turnaround, but after startup, we began experiencing
high levels of amine in the water phase knockout downstream of the liquid treater. The total
volume of carryover was not much greater than that we experienced in DEA. However, the
MDEA concentration in the water phase was much higher.
The higher amine concentration material was causing problems in our wastewater treating
system. After evaluating the liquid treater and trying to determine that we did not have an
operating problem there. We solved the problem by reducing the amine concentration. Right
now we are operating about 25 wt% MDEA in these two systems and that has reduced the
problem in the water knockout downstream. As far as the gas treater, we have not seen any
problems and we did not see any problems at 40% either.
GENTRY:
For background information, we have individual amine systems and contactors on each
major process. Thus, depending on which process, refinery crude diet, and processing severity,
we have switched from MDEA to DEA and also from DEA back to MDEA. The basis for these
decisions are really two objectives, contactor performance and cost. Since DEA is the most
economical, we will always move to this amine as long as satisfactory contactor performance can
be achieved and as long as CO2 absorption is not a limiting factor.
We do have processes where either the gas rate has substantially increased and the
process stream composition has significantly changed. This has required us to move to MDEA to
allow us to run a high strength amine and not cause additional corrosion in the contactor system.
Currently, we are operating some systems with concentrations up to 35%.
JACKSON:
Typical amine concentrations are limited to 18 wt% for MEA, 30 wt% for DEA, 27 wt%
for DIPA, and 50 wt% for MDEA and MDEA-based formulated solvents. The primary concern
limiting concentration is corrosion or concerns over the losses seen from a particular liquid-
liquid amine contactor, usually the result of poor amine-hydrocarbon separation issues. While in
the past most conversions were justified based on reduced energy usage or increased CO2
slippage, today conversions are more often driven by required additional capacities. The amine
strength is selected to minimize circulation rates, subject to equilibrium and loading concerns
(i.e., maintaining a rich loading of < 0.5 mole/mole) while maximizing removal and meeting the
desired sweet product conditions.
One of our Asian clients was using a DGA and decided to switch back to a DEA because
of high solution loses (foaming). The cost of the DGA was approximately 4 times that of DEA.
In their situation they were treating an LPG stream with low levels of COS and saw no advantage
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in removal efficiencies between the two amines. Amine concentrations were the same at around
20-25 wt%.
JAMES D. WEITH (Fluor Daniel, Inc.):

Were any of these switches done on line, such as a flying switch? Or were you shut
down, and had plenty of time to change out the inventory from one solvent to another?
TURPIN:
In the case I referred to, the solvent switch was not done on-line.
GENTRY:
Our changes have been online.

The minimum operating concentration of an amine system can be determined by the acid
gas load for each treater. Knowing the acid gas content and volume of each gas or liquid to be
treated and the available amine circulation, the concentration necessary to limit the rich loading
for each treater can be calculated. The nominal rich loading limit is 0.45 moles acid gas/mole
amine. The minimum amine concentration for the system permits all of the treating applications
to be satisfied. Operating at a minimum concentration reduces physical losses, but restricts the
total acid gas removal capacity of the system.
The maximum operating concentration of an amine system is that concentration where
corrosion or physical properties begins to negatively affect the system’s performance. The
nominal limit for MEA is 18 wt% and for DEA is 28 wt% due to corrosion. MDEA in liquid
treating systems should be limited to 40 wt% to limit losses due to solubility and viscosity.
The question of changing amine in a system typically occurs when the treating demands
increase such that the choice is to operate at higher rich loadings or higher amine concentrations
than recommended. In that case, the following amine concentrations provide equivalent acid gas
removal capacity:
Equivalent Concentration Maximum Recommended Concentration

MEA 18 wt% 18
DEA 30 wt% 30
MDEA 34 wt% 40
DIPA 38 wt% 40
Comparing these values to the recommended concentration limits, one can see that there
is an advantage in additional treating capacity in converting from any of the amines to MDEA.
The added feature is that if appreciable amounts of CO2 are in the feed gases, additional H2S
capacity is afforded by the selective ability of MDEA to remove H2S preferentially over CO2.

In the past mechanical fixes, such as water wash loops and coalescers, were often used in
integrated systems to mitigate the effects of high amine losses in liquid-liquid treaters and allow the
benefits of higher amine concentrations to be realized in the gas-liquid treaters. However, it was still
12
1998 TOC
found necessary to limit solvent concentrations below those noted above. For instance, MDEA was
often limited to less than 40 wt%. New solvents have recently been commercialized which allow
concentrations of up to 50 wt% to be used in liquid-liquid service without concern for excessive
entrainment or solubility. This allows the benefits of 50 wt% formulated products to be realized
across the whole integrated system.
Question 5.
How much CO2 is normally present in combined acid gases produced in refinery
amine systems, and how much can the CO2 concentration be decreased by
switching to a more selective amine? To what extent can Claus plant pressure drop
be decreased by reducing the concentration of CO2 in the acid gas?
TURPIN:
The primary amines (MEA, DGA) have a higher selective to remove CO2 from a sour gas
than the secondary amines (DEA, DIPA), which have a higher selectivity than the tertiary amines
(TEA, MDEA). Switching from MEA to MDEA for example will shift the CO2 pickup from
nearly 100% to 6-12%. The specialty solvents such as Sulfinol (high affinity for CO2) and
UCARSOL (low affinity for CO2) go from one extreme to the other in CO2 selectivity.
Another option for changing CO2 selectivity is to use mixes of amines such as
MEA/MDEA. Temperatures and pressures can also be manipulated to change CO2 selectivity.
The reduction in pressure drop due to removing a portion of the CO2 from the acid gas
can be approximated by multiplying the present pressure drop the square root of the change in
flow rate divided by the total acid gas plus combustion gas flow rate.
A couple of good articles on the subject of alternate amine usage are:
• “Alkanolamine Treating”, Butwell, Kubek and Sigmund, Hydrocarbon Processing, March
1982
• “Converting to DEA/MDEA Mix Ups Sweetening Capacity”, Spears, Haga, Bullin and
Michalik, Oil and Gas Journal, August 12, 1996
• “A Nonrandom Two-Liquid Model for Alkanolamine-Water Systems”, Mark Posey and Gary
T. Rochelle, Presented at the 44th Canadian Chemical Engineering Conference
SMITH:
We do not measure CO2 at Valero. We want to reduce the ammonia load, which is more
beneficial than removing CO2. We are looking at options to convert ammonia into a saleable
product.
LAMB:
I think in this question it depends where you are coming from. A lot of refineries will find
that the CO2 content in the acid gas is 5 percent or less. And in that case, switching to a more
selective amine probably would not yield many hydraulic benefits in the sulfur plant.
A previous Q&A session indicated that one refiner was operating with a CO2 content of
30 percent and switched from MEA to MDEA and lowered that content down to about half and
saw big benefits in the hydraulics of the sulfur plant. So again it depends on where you are
starting from.
13
1998 TOC

The ratio of H2S to CO2 in typical refinery gases is usually high enough to provide a
Claus feed of more than 70 % H2S. Using the typical selectivity of MDEA, this ratio can be
increased to 90 %.
TOFIK KHANMAMEDOV (The Tofik K. Khanmamedov Company):

There is a new patented family of HIGHSULF™ processes that allows refiners to
decrease CO2 concentration in acid gases by using generic MDEA in the amine unit. For
example, the CO2 concentration in acid gas can be reduced from 57.3% to 47.1% for gas plants,
and from 79.11% to 68.4% for gasifier. The CO2 concentration in acid gas of SCOT type tail gas
treating units can be reduced by about 10% in a generic MDEA amine system. Besides these, the
HIGHSULF™ process significantly reduces concentrations of hydrocarbons, COS, CO, H2 in
acid gases of gas plant, gasifier and refinery.
HIGHSULF™ controls the hydraulic loading of the sulfur recovery unit. The reduction of
CO2 concentration in acid gases of main amine units reduces pressure drop of sulfur unit and
leads to capacity increases of sulfur unit minimum by 3%. Reduction of CO2 concentration in
acid gas of SCOT type tail gas treating unit also leads to reduction of pressure drop of sulfur unit
and the capacity of sulfur unit can also be increased at least by 3%. For sulfur recovery units with
oxygen injection configuration the reduction of CO2 concentration in acid gas (main amine and
tail gas treating units) will translate to reduced oxygen consumption or increased throughput at
the same oxygen consumption level.
The HIGHSULF™ tail gas treating process increases CO2 rejection in the absorber and
may reduce the lean amine cooling requirements. This translates to reduced utility cost for an
existing tail gas treating unit or reduced equipment cost for a new unit. The application of the
HIGHSULF™ process is based on utilizing existing equipment and solvents (amine). A
significant advantage of HIGHSULF™ is attaining the same level of CO2 rejection with generic
amines that are attained with specialty amines. This translates into significant amine savings,
particularly where losses are high. Justification of this process is based on computer simulations
by using different commercially available and well proven simulators.

Typically a refinery acid gas feed to a Claus process is in the 50-100 mol% H2S range and
can be accommodated in a straight-through configuration. If the concentration is in the 20-50% range
then a split-flow Claus configuration would be required but this is less common in the refineries as
the number of unit operations producing significant levels of CO2 is limited.
By way of example, consider a refinery using MEA or DEA and achieving essentially
complete CO2 removal and producing a Claus feed of 60 mol% H2S and 40 mol% CO2 (an
oversimplification). Switching to a more selective amine such as MDEA might be expected to reduce
the CO2 pickup by 60%. The resulting Claus feed would be about 79 mol% H2S and 21mol% CO2
- and the overall volume would be reduced by about 24%. If a more selective formulated solvent
such as UCARSOL® Solvent HS-115 is used the overall CO2 pickup could be reduced even further
to around 66%, with the result that the Claus feed would be about 82 mol% H2S and 18 mol% CO2,
reducing the overall volume by about 26%. Actual CO2 removal rates are a function of the partial
pressures involved and the number of absorber stages, amongst other things, but this simple analysis
gives an idea of the impact of using a selective amine on the Claus feed composition and volume
14
1998 TOC
(hence pressure drop).
Sulfur Plants
Question 6.
Who is running 28 percent oxygen or above in sulfur plants? Have any
problems been encountered running above 28 percent oxygen? Does this
practice have an impact on unit vibration?
GENTRY:
At our Port Arthur refinery, we are running currently 33 mole percent O2 and we have
been running that concentration for approximately four years now on two separate 200 ton per
day units. We have not seen any associated problems from the standpoint of mechanical
vibration, nor from process variables. Mainly, this is accomplished by closely monitoring thermal
reactor temperatures to make certain that temperatures do not exceed the operating limits of the
unit.
SMITH:
On our train-2 in Corpus Christi, we run about 28% O2 with no problems. We typically
run 38 to 40% O2. We have no vibration problems on that train. However, our burner tip design
does need to be improved. Also, be careful of your refractory. It can develop hot spots just
around pipe nozzles. Our train-1 cannot operate above 28% O2 because of temperature
limitations of the equipment.

We have applied our Oxygen Injection technology in 18 sulfur recovery units
worldwide. This technology has been successful in oxygen enhanced regimes that range from
28% to 60% equivalent oxygen, with capacity increases as high as 2 times the original nameplate
air based capacity.
With regard to unit vibration, TPA has seen units experience problems at equivalent
oxygen levels as low as 25%. These problems are generally attributed to the geometry of the
main acid gas burner. Note that flame speed increases as the equivalent oxygen increases.
Further, the air rate decreases resulting in lower forward velocities (gas velocity at or below
flame speed). In some burners, this decrease in velocities is substantial enough to permit back
propagation of the flame (burn back). When this occurs, the gases ignited in the burner throat
expand quickly thus temporarily increasing the forward velocity (gas velocity greater than flame
speed). This back propagation/ignition/gas expansion is cyclical, and is most likely the source of
the unit vibration.
RAGHU MENON (BOC):

We have placed in operation two SURETM Double Combustion plants, which can use up
to 100% oxygen which corresponds to 2.5 times the base sulfur recovery capacity. The plant
locations are at Koa Oil in Osaka, Japan and API in Falconara, Italy. Two more plants are
scheduled to come onstream in the next few months, which will operate with 100% oxygen. One
15
1998 TOC
is expected to start up in December 1998, and the other one in the first quarter of 1999. In
addition to these plants, one definite project has been awarded which will be onstream in 1999
using 100% oxygen. Two more have been through the technology selection process, awaiting
capital approval and will be onstream in the next 24 months.
In summary, five out of these seven SURETM Double Combustion technology units will
be operated at 100% O2. In addition, there are several SURETM burner systems operating at
moderate to high levels of O2 enrichment without any vibration problems.
STEVE FENDERSON (Goar, Allison & Associates, Inc.):

There are 17 SRU Trains utilizing the COPETM Process. All 17 trains are operating with
oxygen enrichment levels above 28%. Seven trains typically operate with enrichment levels of
55-100% oxygen. The first COPETM trains began operation in 1985. The 17 trains have a
combined experience of over 100 train years.
One location retrofitted with the COPETM Process exceeded the design oxygen
enrichment limit and design capacity. The waste heat boiler was overloaded, and some tubes
were damaged.
Some burners experience flame stability problems during oxygen enriched operation.
This flame instability is usually exhibited as vibration. The flame stability problem has been
observed in some burners using simple oxygen enrichment of the combustion air at levels as low
as 24% oxygen.
ASHA MASOHAN (Indian Institute of Petroleum):

The Lurgi OxyClaus process uses above 28% oxygen. Ten Claus sulfur recovery units
with OxyClaus are in operation in U.S., and Europe and twelve additional units are currently in
design/ construction throughout the world. The process has been successfully demonstrated in the
United States at Shell Oil Company and Amoco Oil Company. The OxyClaus process offers:
• Economic advantage in case of revamping existing units for added capacity and
constructing new units where redundant capacity is necessary.
• Operating benefits, especially when processing conventionally difficult
lean acid gases often associated with natural gas or syngas processing.
ROBERT BEST (Air Products and Chemicals Inc.):

SRU plant operators who desire capacity increases generally above 30% from air base
operations need oxygen enrichment above 28 mol%. Air Products has commercially
demonstrated a full offering of oxygen enrichment capabilities including low level (to 28% O2),
mid level (28-40% O2), and high level enrichment (40-100% O2). This includes our COPETM
technology (Claus Oxygen - based Process Expansion) which is employed in both mid and high
level enrichment programs. The COPETM process is successfully used in 17 SRU trains to
perform mid to high level enrichment. The following chart illustrates how SRU capacity can
increase with oxygen for typical acid gas loadings.
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1998 TOC
SRU Capacity Increase With Oxygen
160
COPETM RETROFIT
COPETM BURNER
% INCREASED CAPACITY
92% H2S
DIFFUSER
120
70% H2S
80 50% H2S
LLE MLE
40
BASE 0
20 40 60 80 100
OXYGEN ENRICHMENT (MOL %)
Illustrates the level of oxygen enrichment needed to produce an increase in SRU acid gas capacity and shows the
TM
transition points from low, medium and high enrichment level technologies. COPE Retrofit recycles gas back to
the burner from the #1 condenser outlet.
We are aware that problems have occurred with other types of oxygen enrichment
technologies. The most common problems to guard against are:
• Excessive temperatures in the reaction furnace combined with unsuitable

refractory material.
• Unreacted oxygen reaching the waste heat boiler and causing oxidation and
thermal damage to the tubes and tubesheet. This problem is normally associated
with a burner having poor mixing characteristics.
• Refractory damage at hot spots in the furnace caused by a burner having poor
mixing characteristics.
Vibration problems have not been experienced with the COPETM process at either mid
level or high level enrichment. Reaction furnace vibration is most often caused by flame
instability in burners with poor mixing or burners not designed for oxygen enrichment. The
COPETM process Duiker burner produces a stable flame over a wide range of acid gas
17
1998 TOC
compositions and turndown ratios.
Question 7.
What ammonia percentage are you able to reliably burn in your SRU? What
conditions do you consider key to effective ammonia destruction?
GENTRY:
Currently, we are burning up to 5.5% ammonia. Both units were designed for that rate
and we have been able to achieve it. They are Goar, Allison COPE™ Phase I Technology. The
key process parameters for proper ammonia destruction are proper air-to-acid gas ratio and a
furnace firing temperature above 2,300°F. The firing temperature was the main driver behind
incorporating oxygen into this sulfur recovery unit as we discussed in the previous question.
One additional point I would like to make is that the residual ammonia should be
maintained at 30 ppm or less in the reaction furnace effluent to prevent solid deposition in the
unit. This residual ammonia is most affected by ratio control.
SMITH:
The ammonia percentages off of our sour water stripper are normally 25-50%. This
stream goes to our Train-2, which has oxygen injection. We target 2,200°F minimum.
Normally, we are at 2,300°F or higher. Sometimes we will run up to 2,600°F.
WALDRON:
At one of our refineries, the SRU feed is typically 27 percent dry basis ammonia with a
maximum up to 32 percent. The units are Parson split feed design, which divides the amine gas
into the dedicated side burner with the remainder in the front with the sour water stripper gas.
The key is proper control of the side split to maintain reaction furnace temperature at
about 2,300ºF.
JOHN BOURDON (Black & Veatch Pritchard, Inc.):

A plant in Northern California is running and was designed for 45% ammonia in the feed.
That is the combined feed, not just the sour water stripper gas feed. Performance testing has
indicated that it is adequately destroying the ammonia and I agree that has to be basically
non-detectable at the exit to the thermal reactor.
The key design parameters, which were used, were the three T's that are commonly talked
about, time, temperature and turbulence. The residence time needs to be somewhere between a
second and two seconds. As for temperatures, Peter Clark of ASRL has recently completed some
work, that says, if you are not in excess of 2,400ΕF you will probably have some problems. That
depends on the last which is turbulence, i.e., the better the burner, the better the destruction of
ammonia.
RAGHU MENON (BOC):

We believe key factors for destruction of ammonia and other impurities are the furnace
temperature, burner design and availability of oxygen for destroying ammonia and other
impurities. The best process options are (i) the split feed Parsons bypass operation, and (ii) O2
enrichment operation. We have a pilot 1,000 tons per year SRU operating with 30% plus
18
1998 TOC
ammonia in the feed. A comprehensive discussion of this, including very extensive results from
pilot unit testing such as spot-by-spot gas analysis was presented at the Brimstone Conference in
Vale recently by Dr. S. Graville and co-authors.
STEVEN FENDERSON (Goar, Allison & Associates, Inc.):

Ammonia destruction can be guaranteed at concentrations up to 25% ammonia in the
combined feed to the SRU using the Comprimo (Stork) process. The keys to ammonia
destruction are the main burner design, furnace temperature, air control, and furnace residence
time.
Question 8.
What techniques have you found to speed up the cool down on an SRU without
compromising safely, catalyst performance, or unit integrity?
WALDRON:
We typically do initial cool down with the air blower followed by additional cool down
and purge with pipeline nitrogen. If we are pressed for time and want to do it faster, we bring in
truck nitrogen to finish the cool down.
SMITH:
We have not tried any unique ways for speeding up our shutdowns. Typically, it takes
2 1/2 days, including the cool down. We are looking at ways to improve this. I understand that
maximizing air rate using cooled nitrogen as an additional inert under stoichiometric conditions
has been used successfully. The important point is to control flows so that stoichiometric
conditions are maintained while cooling down.

At the Brimstone Conference last week, one of the Ortloff representatives presented a
technique being used by approximately 20 of their plants which is called a cold bed operation.
They actually have a bypass in front of the catalyst reactors. They are bypassing the catalyst
reactors, letting them cool down independently. They then start up through the front of the
system, going directly to the incinerator, and starting the catalyst reactors cold rather than hot.
They introduce acid gas and allow the thermal rise to run through the beds and heat up at the
same time. Although this is somewhat new to our industry, it is a way to cut the time for startup
and shutdown significantly. I would be interested in any feedback from people that are using this
technique.

Nitrogen sweep of the SRU has been used to speed up cool down. Caution should be
used to avoid cooling the burner and reaction furnace refractory too rapidly or the refractory can
be damaged.
ROBERT BEST (Air Products and Chemicals Inc.):

Air Products has been of service with the cooldown of sulfur recovery units during
turnarounds by providing nitrogen gas and nitrogen pumping equipment services. Our pumping
19
1998 TOC
units deliver vaporized liquid nitrogen at approximately 40-50°F to the acid gas inlet port of the
burner. From this feed point, the cool nitrogen stream passes through the SRU train on a once
through basis, then exits out the flare. The nitrogen gas provides cooling while offering an inert
gas purging atmosphere for safe shutdown operations.
A typical SRU cool down has required 0.5-1.0 mmscf of nitrogen to perform the cool
down which normally takes between 6-10 hours to complete. The actual volume of gas
consumed and the rate of cool down will be highly dependent on the capacity or size of the SRU
plant.
Turnaround Sulfur Recovery Unit

Cooldown
Burner Reaction WHB

Furnace Steam
Combustion Air To
Downstream
Processing
• Amine Acid Gas

• Sour Water
Stripper Gas
• Tail Gas BFW
Nitrogen
Pumping Unit
o
40 F Nitrogen
REF102- 1
Question 9.
Are there any operating units with catalysts other than aluminum oxide
Claus catalysts and what are the benefits? Are there advantages in using
titanium oxide Claus catalysts over conventional aluminum oxide Claus
catalysts in sulfur plants?
RASBOLD:
Sun has sulfur plants in our Philadelphia, Toledo and Yabucoa refineries. All of our
Claus plants utilize alumina, or promoted alumina, catalysts. However, our Research and
Development group has studied titanium catalysts. What they indicate is that, while the titanium
catalyst is more expensive, you get higher activity and higher conversion of carbonyl sulfide and
carbon disulfide, which are very difficult reactions to achieve. If your plant sends the Claus tail
gas directly to an incinerator, unconverted COS and CS2 could increase your sulfur emissions. If
your plant treats the tail gas before an incinerator, these unconverted sulfur compounds are
20
1998 TOC
converted back to H2S and recycled to Claus, potentially overloading your unit. In addition,
titanium catalysts are highly resistant to sulfation, which would tend to block alumina catalyst
pores and therefore decrease activity.
ALLEN:
The only thing that I wanted to add to Mr. Rasbold’s response was that titanium dioxide
catalysts are about four to five times more expensive and that the information I have is that you
can basically solve the same problem by proper monitoring control using conventional catalysts.

The panel did mention the higher activities and higher COS and CS2 destruction when
using titanium oxide catalyst. Quantitatively, COS/CS2 destruction with conventional aluminum
oxide catalyst is approximately 60% (temperature dependant). Titanium oxide catalyst is capable
of COS/CS2 destruction efficiencies in excess of 90%. The use of titanium oxide catalyst
facilitates a lower catalytic reactor temperature, which increases Claus reaction efficiency. This
higher Claus reaction efficiency coupled with the higher COS/CS2 destruction efficiency results
in incrementally higher unit recovery efficiencies (typically 0.5% to 1.0% higher).

Many plants are operating with titanium oxide catalyst. The titanium oxide catalyst
improves COS and CS2 conversion in the first reactor. Titanium oxide catalyst is resistant to
deactivation by sulfation and can be operated at a space velocity of up to 1200 SCF gas/ft3
catalyst.
PAUL VANCE (Acreon Catalysts):

Several units are operating in Claus units using titanium oxide catalysts
(Acreon/Procatalyse CRS-31). These units are in very demanding conditions and have
demonstrated performance beyond the capability of an aluminum oxide catalyst. One unit uses a
hot gas bypass reheat for the #3 converter and with substantially increased conversion of
COS/CS2 over that found with the prior aluminum oxide catalyst. Other units now have
increased sulfur capacity with CRS-31 in either the #1 or #3 converter with improved conversion
of COS/CS2. Only titanium oxide can provide stable conversion and longer catalyst life in
environments where aluminum oxide catalyst would be sulfated since sulfation does not occur
with TiO2 catalyst. Other advantages include longer catalyst life, higher overall sulfur
conversion in the Claus unit, and reduced load to the tail gas unit. These performance deltas
have been successfully guaranteed in several units worldwide. In another unit, Claus capacity
was increased due to lower required catalyst volumes, higher GHSV, and stable high conversions
levels for H2S, COS, and CS2 for a very economical capacity increase to an existing unit.
Question 10.
Are any of the panelists aware of a process that converts H2S or SO2 from
sour gas or incinerator off gas respectively into sulfuric acid, without first
going through Claus process? If so, what is the feasibility of such a process,
and also give references?
21
1998 TOC
LAMB:
I assume the origin of the question is how to get some value out of your sulfur since the
price of sulfur is not very high these days. Both H2S and SO2 can be potential feeds to an acid
plant. In the case of SO2, the feed gas normally has to be heated by heat exchange or with
another fuel to get it up to the reaction temperature for converting it to sulfur trioxide. In the case
of H2S, it is a good fuel and does not require any supplemental fuels.
Some of the things you need to consider with an acid plant include maintaining the
reliability you have with your Claus plant today, which may mean you are looking at a Claus
plant in addition to an acid plant. You may also be looking at two acid plants or a very deluxe
acid plant to make sure you do not have any air pollution when the plant comes down.
Size is a question that often has to be considered, i.e., is there a big enough market within
100 or 200 miles of your plant? How would your plant compare to the competition? Is your
refinery remote to sulfuric acid supplies; i.e., located more than 200 miles from nearest source of
supply?
Some of the acid plant vendors who can give you a lot more information would be
Monsanto Enviro-Chem, Acid Engineering, Chemetics (Canadian), Lurgi, Grande Paroisse
(French), and Haldor Topsoe.

One such process is KVT-Sulfox. Depending on the raw gas H2S/SO2 concentration, it is
possible to produce sulphuric acid of capacities up to 100 tpd and concentration above 96%. A
brief description of this process is given below.
The process is based on a two-bed catalytic oxidation process. The first catalytic bed
consists of a proprietary catalyst, which converts CS2 and H2S to SO2 and is also able to convert
the major part of SO2 to SO3. The remainder SO2 is converted to SO3 in a second catalytic bed
consisting of commercial vanadium catalyst. After the reaction, the treated gases are cooled in
two recovery heat exchangers and the sulphuric acid is then recovered by condensation in the
electrostatic filter. The cleaned gases, which are in full compliance with TA-Luft regulations, go
to atmosphere.
Depending upon the feed gas concentration, one can choose the following:
KVT-Sulfox NK: for sulphur compound concentration in raw gas from 1,200-5,500 ppm.
KVT-Sulfox HK: for concentration above 5,500 ppm
KVT-Sulfox REG: for concentration between 100 to 1,200 ppm
Due to operation above the acid dew point, there is a choice of economic and better
materials of construction, and thus investment costs are 30% less compared to conventional
processes. Depending on raw gas concentration steam may be generated. One plant has been
operating successfully since 1993 and several confidential feasibility studies are claimed to have
been carried out.
Reference: Man-Made Fiber Year Book (CTI) 1994, "Desulphurisation of waste air in viscose
industry with recovery of sulphuric acid"; cf: Hydrocarbon Processing, p 125, April 1996.
Licensor: KVT-Kanzler Verfahrenstechnik GmbH and Ing. A. MAURER S.A.
22
1998 TOC
Question 11.
Does SRU performance vary with changes in velocity in the condenser?
RASBOLD:
Our Philadelphia refinery sulfur plant performance is affected significantly by velocity
changes in the sulfur condensers. We presently run on a 10:1 turndown ratio as we currently
make 22 tons/day elemental sulfur, and our two Sulfur Recovery Unit trains were designed to
extract 100 and 120 tons per day. One train is currently operating with the second on hot standby.
There are two problems we experience with low velocities. The first is sulfur fogging
which occurs when the local temperature in the condenser reaches the dew point of sulfur. This
condensation can occur in the gas stream and not on the walls of the condenser tubes as designed
and reduces the once through efficiency of the unit.
The second problem stems from the higher tendency for the condensers to plug due to
low velocity. This creates a system backpressure, which reduces our ability to get air into the
system for our combustion air blower.

SRU performance is definitely affected if condenser tube velocities are too high or too
low. Excessive velocities can entrain condensed liquid sulfur in the process gas and carry it to
the next reactor, tail gas unit, or incinerator. Velocities that are too low can result in sulfur fog
formation. Sulfur fog occurs when sulfur is condensed in the bulk gas instead of on the tube
wall. The sulfur fog droplets are so small they are not separated from the gas, but are carried
through mist eliminators to the downstream reactor, tail gas unit or incinerator.
The condenser mass velocity operating range should be between about 1.5-5.5 lb/sec-ft2.
Mass velocities below 1.0 and above 6.0 lb/sec-ft2 can result in sulfur fog or entrainment,
respectively.

SRU performance can vary with changes in velocities through the condenser tubes. Low
condenser tube velocities can produce a "sulfur fog", which is the result of condensation
occurring in the gas stream instead of on the tube surface. This "fog" is difficult to separate in a
condenser plenum, and it is carried over into the catalytic reactor and/or the downstream facilities
(TGTU or incinerator).
This problem can be remedied by evaluating the condenser and plugging condenser tubes
to facilitate tube wall condensation. Further, liquid sulfur carry over should be addressed by
evaluating the separation efficiency of the condenser plenums. It is worth noting that many
sulfur condenser plenums are too small to be effective gravity separators, and therefore need a
device, which will enhance the liquid/vapor separation. We have successfully applied a device
called the SulfSep Entrainment Separator on several units to minimize liquid sulfur carry over,
with results that are most impressive. The application of these devices resulted in substantially
lower incinerator SO2 emissions on a unit not equipped with a tail gas treater (recovery efficiency
increases have ranged from 0.2% to 1.0%). They have served to improve the reliability of the tail
gas ratio analyzer by off-loading the sample system of excessive liquid sulfur.
23
1998 TOC
Tail Gas Plants
Question 12.
Is anyone considering a tail gas unit that recycles sulfur dioxide instead of
hydrogen sulfide? If so, which technologies are considered commercially
proven?
LAMB:
I can cover the second part of the question. There are two technologies people are
considering for the purpose of recycling SO2 back to the front end of a Claus plant. The first one
is by Linde AG, which is the Clintox process that uses a physical absorbent. There are four
plants now in operation on flue gas, so it is commercially proven. There are none that recycle
back to the front end of a Claus plant. Reportedly, if you recycle SO2 back to the front of the
Claus plant, you can get 99.9% recovery of sulfur which corresponds to a sulfur content in the
Claus plant effluent gas of about 100 ppm. Also, this process can be used to increase the
capacity of your existing Claus plant. If you are looking at a new installation, many times it
would make sense to cut some cost in the Claus plant by having less reaction stages.
Also, there is a ClausMaster process being promoted by Monsanto’s Envirochem Systems
Division similar to the Clintox process. It also uses a physical absorbent. They claim it is ready
for commercialization. At this point in time, there are no plants in operation.

Monsanto Envirochem is offering their ClausMaster process for tail gas cleanup. The
ClausMaster process uses a physical solvent to absorb SO2 from incinerated SRU tail gas. The
solvent is regenerated and SO2 is recycled to the SRU.

The Clintox process of Linde AG recovers SO2 from Claus tail gas and recycles it to the
Claus unit. As an add-on unit to the existing Claus plant, the Clintox process increases both the
capacity and capability of the system. A brief description is given below:
The process uses a physical scrubbing mechanism to remove SO2 from the tail gas of a
Claus unit. The recovered SO2 is recycled to the inlet of the Claus unit. It is claimed that since
the efficiency of the Clintox physical scrubber increases when the tail gas SO2 concentration
increases, a less efficient Claus unit can be tolerated. Thus a combination of Claus and
Clintox units gives a sulphur recovery system that is self-regulating, to an extent, allowing
sulphur recovery rates in excess of 99.9%, or emissions below 100 ppm. Investment and
operating costs of the Clintox process compare favorably with other conventional processes.
There are four installations in Western Europe.
Reference:
1. MP Heisel and FJ Marold, "How new tail gas treater increases Claus unit
thruput", Hydrocarbon Processing, Vol. 71, No. 3, p83, March 1992.
2. "Clintox process", Hydrocarbon Processing, P 111, April
1996.
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1998 TOC
HUGO BILILONI (Biopari, Argentina):

There is a new SO2 removal process developed by the gas division of Dow Chemicals and
currently being licensed by a company named Tourvisac.
Question 13.
What analyzers are being used for monitoring and control of tail gas units?
SMITH:
This question was covered by Mr. Dale Hansen of Valero in the 1995 NPRA Q&A
transcript. I will read an excerpt from it. “We use Ametek Model 4620B solid state photometric
analyzers to measure the excess H2S in the Claus Unit tail gases and control combustion air flow.
Excess hydrogen in the amine absorber exit gas is successfully measured using a Beckman
Model 7C thermal conductivity type analyzer. Direct hydrogen injection is flow controlled with
set point changes initiated by the operators based on excess hydrogen measured. The quench
loop pH is measured and monitored on the control board by a Rosemont model 1181 pH
analyzer. Anhydrous ammonia on board mounted flow control is available to temporarily aid pH
when upset conditions occur. A bull’s eye type sight glass is installed in the loop so that the
outside unit operators can monitor water appearance. Cloudy or black water are signs of SO2
breakthrough”.
Since then, we have added an additional two instruments to the gas leaving the tail gas
unit. We have another Ametek model 4600 series SO2 monitor, and we have Siemens model
Oxymat 5F for O2 analysis.
TRAEGER:
Our experience is similar. In our opinion, the most critical analyzer for the stable
operation of the tail gas unit is the H2S/SO2 analyzer that is upstream in the Claus unit. We
utilize also an Ametek 4620 photometric analyzer, which has been very reliable. We have also
had some good luck recently, although not in front of a tail gas unit but on our other sulfur units
with a newer model of the Ametek analyzer that mounts directly to the process piping,
eliminating potentially problematic sample lines.
For the excess hydrogen content on the tail gas reactor, we utilize an applied automation
Caldos 5G, which is a thermo conductivity analyzer. Additionally, we have recently switched to a
ceramic coated pH probe from Yokogawa for monitoring the circulating water in the tail gas
quench tower.

Cansolv, which is an amine based SO2 technology developed in the mid-80s, is now
being marketed by Cansolv Technologies, Inc. out of Montreal, Canada. A demonstration plant
was originally run for nine months in Canada. A new demonstration plant has just been operated
in Florida. The technology should be commercialized next year. It is a regenerable amine based
SO2 technology that works very much like MDEA.
There are two specific advancements in the area. One would be that it is specifically
applicable to scrub FCC off gases and to recycle the SO2 to the Claus plant that enables the
second advance, that is, to eliminate the thermal section of the Claus plant. Both advancements
should significantly impact the way we treat sulfur in the future.
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1998 TOC
Responding Question 13, Brimstone Engineering out of either Denver, Colorado or

Calgary, Canada, has an in situ analyzer, tail gas analyzer that mounts directly to a flange. There
is no sampling system. It is based on an optical system that does not have sample lines to plug.
Plugged sample lines are traditionally the problem.
B. Environmental Management
Air
Question 14.
What is the panel's experience with Continuous Emissions Monitoring
Systems (CEMS) in the refinery, and on FCC stacks in particular?
RASBOLD:
As far as FCC stacks, at our Philadelphia plant, we have a CEMS on the Point Breeze
FCC stack that measures SOx and NOx. We also have one on the Girard Point FCC stack that
monitors NOx, carbon monoxide, opacity and oxygen. These analyzers are calibrated daily by our
instrumentation group. Our Marcus Hook FCC plant has a CEMS for sulfur dioxide and opacity
on the stack and undergoes weekly preventive maintenance and calibration by our instrument
technicians. Finally, our Toledo refinery has an opacity monitor on its FCC stack and is checked
quarterly by a factory representative. All FCC stack CEMS at these plants have onstream
reliability factors ranging from 95-99%. Also, our analytical performance based on actuals versus
the calibration indicate very good performance at all of our locations.
In addition, as far as other refinery uses, our Tulsa refinery utilizes a CEMS on our truck
loading dock vapor recovery vent for MACT requirements. This analyzer detects hydrocarbon
emissions as propane, calculates and records these as emissions in milliliters of hydrocarbon per
liter of product loaded. This analyzer was installed in March 1998, and there has not been any
negative analytical or reliability performance issues to date.
SMITH:
Valero’s environmental department graciously provided this answer for me. We have
numerous CEMS in the refinery - NOx and CO on heaters and boilers, fuel gas H2S, SO2 on
sulfur plant tail gas incinerators, VOC on the marine vapor recovery unit, and SO2, CO and NOx
on the FCC stack. The most important consideration in selecting of CEMS is to use a well
known, established manufacturer that you or similar facilities have had good experience. We do
not use package systems. For example, we purchase the pollutant analyzers and O2 analyzers
separately, and we use our computer for data collection and reporting.
Our installations always include locating the CEMS in an air conditioned building. The
key to satisfactory operation of the instruments is a good sample conditioning system.
We have a wet scrubber on our cat cracker, so it is essential to remove significant
amounts of water from the sample. We accomplish this with a vortex cooler and knockout pots.
In-line filters are also needed to prevent pluggage in the sampling system.
Important aspects of maintaining CEMS include having a reliable source of calibration
gases and implementing a good PM program, checking the analyzers daily, draining water from
26
1998 TOC
the knockout pots, changing filters, keeping the systems clean and unplugged. We feel that our
program is successful due to having good instrument technicians that are dedicated full time to
analyzer work.
TRAEGER:
Our experience with CEMS in refineries is that they are expensive and require a large
amount of maintenance time, even when they are operating well. In many cases, the problems we
run into with CEMS are as critical and limiting as any other operating problem we have in the
refinery. Mostly that is because of the restrictive data recovery requirements.
We currently operate CEMS in the following areas: two SRU incinerator stacks, two H2S
in fuel gas monitors, an FCC stack monitor and some fuel oil burning flow meters that we also
feed into our CEMS system.
Additionally, we also bring in fuel gas flowmeters from several of the process heaters to
our data collection package. We calculate emissions based on some fixed emission factors from
that information. Routine maintenance of these systems alone currently requires two full time
technical crafts personnel and additional personnel when problems are encountered.
Our FCC stack CEM is designed to monitor the pounds per hour of SO2 emissions from
the stack. The SO2 concentration analyzer is an Ametek in situ photometric analyzer and the
stack flow meter is an s-type pitot tube design. The FCCU does not operate with an ESP or any
type of third stage separation. As a result, we are concerned about the reliability of this
equipment because of exposure to catalyst fines. The reliability of this equipment has been as
good or better than the other CEMS in the refinery.
GENTRY:
We have analyzers on our FCC unit, refinery fuel gas system, and SCOT units. We
anticipate adding probably about 20 more CEMS approaching the year 2004 because of our
flexible permit. I would agree with the comments that it is generally not the analyzer itself that
gives you the problem. It is either the environment it is placed in or the sampling system that it is
associated with.
MASTRACCI:
As we just heard, there are a large variety of applications in a refinery that require CEMS.
These include FCC flue gas, boilers, heaters, and incinerators.
These analyzers provide information, which is rarely useful for anything other than
environmental compliance. For example, FCC flue gas CEMS provide us the ability to calculate
the regenerator heat balance perhaps a little more accurately than otherwise would be done with
conventional techniques.
The majority of the problems with CEMS stem from the inherent sensitivity of the
instruments and the sample conditioning equipment to various malfunctions. The level of
maintenance staff must be increased in proportion to the number of CEMS installed.
Our Eagle Point refinery has ten Instrument/Electrical technicians covering 96 analyzers.
They in turn are supported by environmental, process, electrical and mechanical engineering as
needed. The technician's duties include routine maintenance and the required regulatory testing
certifications. We feel we are getting good productivity when 9 analyzers are supported per
technician. The technicians are on a seven day, ten hour maintenance schedule. The schedule was
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1998 TOC
adopted partly as an effort to reduce overtime expenses in maintaining the instruments.

I hope everyone knows what CEMS really stands for. It stands for Continuous Expensive
Maintenance Staff. This is the hidden cost of CEMS that the legislators and permit writers do not
often take into account. There is a high price associated with online emission monitoring which
in the final analysis may not offer better quality information than semiannual or quarterly
measurements.
Alternatively, parametric modeling can be used to predict emissions based on previously
established correlations. This approach, unfortunately, shifts the burden (and consequently the
cost of compliance) from maintenance technicians to process or process control engineers. It may
be in the end that this is a little more cost effective.
Question 15.
Do you have environmental or operating permit limits on refinery flares? What
types of flow meters and analyzers are being utilized?
SMITH:
All our flares at Valero are permitted. We have four elevated flares: a main flare, an acid
gas flare, a flare on our MTBE complex and a halo flare. We also have a ground flare. Two of the
flares are permitted for continuous combustion of process vents and the other three are permitted
for emergency use only, (i.e., upset, startups and shutdowns).
We have a panametrics, ultrasonic flowmeter and a gravity analyzer on the main flare.
Other monitoring equipment include: cameras, TV monitors in the control rooms and we also
have ultraviolet sensors to confirm that the pilot and/or flare are lit.
There are numerous regulations and permit conditions applicable to our flares. These
include the following: 1) Conduct daily visual operations to confirm that the flares are not
smoking. 2) We have several process units that are subject to various subparts New Source
Performance Standards (NSPS) and regulations pertaining to hazardous air pollutants. 3) Our
permits contain a condition requiring 98% destruction efficiency which we have documented by
showing that design flow and composition meet the heating value and tip velocity criteria
specified by 40 CFR 60.18. 4) If we have a problem with an SRU train or the tail gas cleanup
unit, acid gas flaring is restricted by our plant permit to not exceed 12 hours in duration.
TRAEGER:
Yes, at this time we are operating with an SO2 pound per hour limitation on our refinery
process flare. The limits are set in the state enforced SO2 reduction plan or SIP. We are limited to
an emission level of 150 pounds per hour of SO2 from the flare tip in any three hour period. A
base level of emissions which must be included in the three hour period has been calculated
using fixed factors for leakage past relief valves. Any additional sulfur bearing streams, which
we send to the flare must be documented. SO2 emissions from those streams are then calculated.
At this time, we are not using any flowmeters or analyzers on the flare header system. We
are just utilizing engineering judgment in calculating the SO2 emission rates.
RASBOLD:
Each of our locations is somewhat different in what is required on our flare systems. Our
Marcus Hook and Philadelphia refineries are located in Pennsylvania, which has a maximum of
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1998 TOC
500 ppm SO2 from any point source. Our flares do fall under this description. All of our
refineries have flare opacity limits. While they have minor differences, in general the limit is to
not exceed 20% except for five minutes per hour, or 20 minutes per day, and to never exceed
60% opacity. All of our flares also utilize flame detection systems, typically a thermocouple, in
order to meet MACT, NSPS or benzene NESHAPS requirements. None of our systems have
experienced success with flowmeters like Mr. Traeger described earlier. They were originally
installed on most of our systems, but all are currently either not utilized, or not reliable.
JACKSON:
One experience at a refinery I am familiar with has their flares included in the refinery
emissions limit bubble. There are no specific limits for the flare itself. The refinery fuel gas
routed to the flare is monitored for hydrogen sulfide with a continuous monitoring gas
chromatography system.
Some of the measuring devices were discussed in 1995. I think both have been mentioned
here, thermal dispersion technology flow-meters, as well as ultrasonic flow-meters. The thermal
dispersion meters have superior accuracy and repeatability, but many times this cannot be
realized due to varying composition of the flare gas. When the composition of the gas changes,
so does the thermal conductivity, which renders the meter factor inaccurate. The same calibration
requirements are necessary for the ultrasonic flow-meters. Some of the suppliers were
Panametrics, Instrumet and Khrone.
RADCLIFFE:
We tried a number of flare measures including Agar probes and even an infrared camera,
primarily focused at trying to calculate flaring loss. None were able to produce a realistic
measurement of gas. We had problems with steam flows and those sorts of things in the flare
header, interfering with meter measurements.
Question 16.
What are refiners doing in preparation for MACT compliance with hydrogen
plant atmospheric process vents?
TRAEGER:
EPA has decided that the MACT analysis and the related cost effectiveness analysis are
not applicable to hydrogen plants CO2 and deaerator vents. The result is that there is now an
exemption from the MACT compliance for both these streams, published in the Federal Register.
JIM ABBOTT (Synetix):

Methanol and amines in hydrogen plant vents, as you stated, are now exempted from
MACT compliance. However, I feel that many people are still thinking that they will be
eventually covered and are making preparations accordingly.
This as a potential problem depends upon the size of the plant, the type of catalyst and
time in service. It also depends on a number of different process conditions, for instance,
pressure, steam ratio on the plant, and knock out pot conditions. It is usually from the low
temperature shift catalyst that the methanol is derived, and it also depends on the high
temperature shift operation as to how much CO is slipping and increasing the temperature in the
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1998 TOC
low temperature shift.

There is quite a bit that can be done to look at the analysis of the methanol to see whether
there is a problem in either of those vents, backed up by simulation of the operation. Ultimately,
if there is a problem, then there is a catalytic solution that can really drive down the levels of
methanol in the vents. We have a new catalyst using inhibition of the methanol selectivity in our
traditional 83 series low temperature shift. That can give more than a fivefold reduction in
methanol production. The important thing is that the shift activity itself is maintained. It is not a
good idea to get the methanol selectivity down, but to lose the ability to operate at low
temperatures.
Because it is a question of methanol being produced at different rates at different times of
a catalyst’s life, another potential option is to look at high temperature shift catalyst and low
temperature shift catalyst scheduling. For instance an old or inactive HTS catalyst combined
with a new LTS catalyst can give the highest methanol formation.
Question 17.
What methods are refiners using to meet MACT standards for sampling
stations?
RASBOLD:
Sun utilizes closed purged sample loops for all streams identified to meet MACT
standards. We use both an in-house design and a Dopak brand system. A Dopak brand has both
closed purge, and closed sampling features. For example, for light components, a metal cylinder
with quick connect attachments is connected to the sampler at both ends and is flushed with the
process stream. This flushing stream returns to the process unit. Once the sample is taken, the
cylinder valves are closed. The remaining hydrocarbon in the sampling system is purged to the
flare, and the cylinder can be removed from the sampler.
For mixed light and heavy hydrocarbons, a sampler similar to those for light ends is used,
but a nitrogen stream purges the remaining hydrocarbon to flare. For liquid components, we use a
sampler with glass bottles and septum caps. The bottle is placed in the sampling unit and two
needles puncture the septum cap. The process stream is flushed through the sampling unit and
back to the process until there is fresh material in the sampling lines. The flow is stopped and
nitrogen forces the sample into the bottle via the first needle. Displaced air in the bottle exits
through the second needle to the flare line.
SMITH:
Most of our sample points are subject to MACT. These are already subject to the NSPS,
Subpart GGG. These sampling stations consist of piping and connectors to purge fluids back to
the process or to the flare. For liquid samples, less than 15 psig vapor pressure, Dopak model
DPM-320Z-221 is used. For vapors and liquids with a vapor pressure greater than 15 psig vapor
pressure, Dopak model 532-30010 is used.
Other factors such as viscosity, temperature, etc., are taken into consideration for
selection of components for these process samplers. All samplers allow constant circulation or
blow down of sample points with a return going back to the process. This allows a fresh sample
to be taken without dumping process material to the environment or to the oily water sewer. All
samplers were installed by August 8th, 1998. However, we are still optimizing heavy liquid
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1998 TOC
samplers under GGG.
GENTRY:
I would like to add that we did process analysis and review on individual streams and
determined that a relatively small number of sample stations actually fall under this MACT
standard.
Water
Question 18.
How do refiners minimize the impact of process leaks into cooling water
systems? What monitoring techniques are used to determine process leaks?
JACKSON:
Responses to minimize the impact of process leaks in the refinery cooling water systems
would include the use of surfactants for improved MB control and dispersion of heavier
hydrocarbons; increased deposit control chemistries for suspended material, metals, calcium
carbonate etc.; supplemental use of non-oxidizing biocides and increased corrosion inhibitors
particularly for copper alloys that may be attacked by the sulfides, and/or the increased use of
chlorine for MB control.
The performance of standard chemistry for a cooling water system can be severely
compromised by the presence of high halogen residuals when trying to solve MB problems .
Several of the chemical treatment companies have introduced a new series of products (Dianodic
PLUS - BetzDearborn product) that are not only more effective but are also completely halogen
stable. This characteristic allows high halogen dosages to be used to address MB issues during
persistent leaks without compromising corrosion or scale control in the system.
Monitoring
•The presence of a leak may be indicated by several factors including:
Change in appearance of the water - color, turbidity or in a bad leak, free oil. An
"experienced" eye is a valuable tool.
•Increasing MB activity, slime formation, difficulty in controlling MB activity.
•Corrosion coupons or deposit monitoring devices may give an indication of increased
corrosion or fouling sometimes seen as a formation of black oxides, which can indicate
the presence of sulfides.
•If "U" (Heat Transfer coefficient) tracking is being done, there may be a sudden drop in
these values.
•Loss of halogen residual or very high halogen consumption to reach a residual.
•Negative shift in ORP controllers for halogen residual.
•High TOC numbers.
•High hydrocarbon readings from vapor space monitors. These devices are
used routinely for leak detection and location and involve "sniffing"
the vapor space above a cooling water sample.
•Difficulty in filtering the water samples in the lab.
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1998 TOC
•Shift in pH from acid or caustic type materials.
Some refineries have occasionally resorted to more exotic methods to "fingerprint" the
hydrocarbon in the water and thereby determine which exchanger or exchangers must be at fault.
More routinely, pH, and conductivity changes and loss of halogen residual across an exchanger
along with the vapor space "sniffers"/bubblers have been the methods used for locating the leak.
Fluoride electrodes can be used in HF alkylation exchangers as well as an indication of
pH depression where small process leaks can be masked by slight decreases in sulfuric acid rates
(monitor additive acid rates closely). The HF alkylation unit typically employs the use of a
separate cooling tower from the rest of the refinery processes to isolate potential damage. Many
refiners now require seal welding the tubes in HF exchangers to prevent roll leaks which can be
the culprit in many situations.
GENTRY:
I would just like to add two points on the monitoring techniques. One of them is operator
visual monitoring. Second, as part of our flexible permit we instituted a refinery wide program of
sampling and analyzing our cooling water supply and return on all eleven towers.
We use our cooling tower chemical vendor to sample these streams each month and we
test them for purgable organic carbon. If the delta POC is greater than 10 ppm, we will check the
exchangers for possible leaks in that system. The normal values of POC are in the range of 0-1
ppm.
RASBOLD:
Our biggest determining factor that indicates if we have a process leak is turbidity of the
cooling water. We monitor both the makeup water and each cooling tower's basin twice a week
to monitor the base level turbidity. We are somewhat careful with this measurement since an
increase could be a simple result of an increase in the solids in the water from another source. We
also use periodic TOC (total organic carbon) monitoring of the cooling tower basins and fixed
hydrocarbon monitors in the vent line on the cooling tower riser as other indicators for leaks. If
we confirm that we do indeed have a leak, then we check each exchanger in that particular
system individually by checking chlorine residual (only if we catch the leak early enough). Other
methods that we use are delta TOC and delta hydrocarbon across each exchanger.
As far as minimizing the effect of the process leak, Mr. Jackson has already detailed the
utilization of surfactants and microbiological control products. Our cooling water treatment
chemical supplier adds dispersants (typically surfactants). Hydrocarbons in the water can coat
heat transfer surfaces in exchangers which restricts heat transfer. Surfactants minimize this
effect. Since hydrocarbon in the water serves as a nutrient for microorganisms within the cooling
water, microbiological control products are increased to control their population growth. In
addition, antifoam is added to the cooling tower to prevent excessive foaming caused by the
addition of surfactants. The foam has a tendency to minimize heat transfer characteristics
typically seen with fine water droplets in the cooling tower itself.
SMITH:
Early detection and repair is the best way to minimize impact of the process leaks. We
use chlorine gas and we add it continuously. Any dip in the chlorine concentration or any
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1998 TOC
increase in the amount needed to maintain the desired concentration will initiate an ORP survey
of the system. The oxidation reduction potential meter is the best tool we have found to locate a
process the leak in the refinery.
TRAEGER:
The only additional thing I could add is relative to monitoring. We perform daily
monitoring of our oil and grease levels via a camphor test method, which seems fairly sensitive. I
know that there are now available continuous monitors for oil and grease monitoring on the
cooling towers. I think reliability of these monitors is still an issue.
ZETLMEISL:
For minimizing impact of process leaks into cooling water systems I would like to
reiterate the recommendations of the other panelists to rely on their chemical supplier for
judicious use of surfactants/bio-dispersants and effective application of microbiocide to
minimize bio growth. As to monitoring, I would also like to reiterate the recommendation of
oxidation reduction potential meters on both supply and return headers. I would also like to
mention that Baker Petrolite incorporates a hydrocarbon vapor collection device, as part of our
DemandTrac™ cooling water treatment program. This device collects vapor from recirculated
water for GC analysis identification. The GC analysis provides a fingerprint of different
hydrocarbon streams, and narrows the search for the leaking exchanger.
CHRIS SPURRELL (Chevron Products Company):

At the Corrosion '96 conference with NACE, there was a paper 610, a new approach to
detect and identify hydrocarbon leaks and refinery cooling systems. It allows ways to speciate the
hydrocarbon to get to exactly the exchanger that is leaking.
Question 19.
Do you discharge neutralized caustic to your biological waste water treatment
system? If so, how do you control and monitor to prevent exceedences in your
waste water discharge limits?
ALLEN:
First of all, thanks to John Foster at Foster-Wheeler in the UK for providing me with
input for this question.
In answer to the first part of the question, yes, neutralized caustic can, and is, discharged
to biological waste water treatment systems. The key to control and monitoring at the discharge
is in understanding the source of the spent caustic and designing the neutralization systems ahead
of the biological treatment plant appropriately.
Caustic is used in a variety of locations in refinery operation and results in 4 major types,
which differ in character and require slightly different handling at the neutralization stage before
sending to biological treatment.
The 4 major types are:-

• Sulphidic caustic – which arises from LPG and Gasoline sweetening processes. The caustic
contains 1000’s of ppms of sulphur, predominantly sodium sulphides/bisulphides and
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1998 TOC
mercaptans. Typically the tolerable sulphide level in the feed to a biotreatment unit will be
less than 20ppm, therefore the rate of addition of this type of spent caustic to the
neutralization system must be carefully controlled.
• Naphthenic caustic – arising from caustic washing of kero and diesel cuts to remove
naphthenic acids. Unfortunately the sodium naphthenate produced is water-soluble which
means that the acid can only be sprung effectively under acid conditions. Inadequate removal
will raise the effluent BOD and exert a toxic effect on the biomass.
• Phenolic – resulting primarily from the removal of acid oils from FCC gasolines. These spent
caustic streams contain phenols, cresols and other organic acids which are generally present
as water-soluble phenolates. As for the naphthenic contaminated caustic, the phenolates will
separate as acid oils at low pH with the same treatment issues as for naphthenic caustics.
• Chloride – usually arises from pH control but usually goes into the sour water stream where
the chloride content is not a significant problem.
Overall the flowrates, strength and composition of caustic streams to the neutralization
unit will vary. The simplest way to control discharge limits is to practice effective blending and
balancing upstream of the neutralization step. The pH may be controlled using measurement of
the blended feed and the neutralized product. Hydrocarbon levels out of the neutralization step
should be monitored to ensure they are being removed effectively.
Ensuring that there is good mixing in the unit is also very important. Providing a small
diversion tank to catch sudden surges in flow or quality or to rerun off-spec product will help to
control the quality of the feed to the neutralization unit.
Diverted flow can be bled back in at a manageable rate after the excursion. This makes
control of the neutralization unit easier and the resultant effluent to the Biotreatment plant a
consistent quality.
Flexible and responsive pH control schemes can be configured in a variety of ways. Care
should be taken to integrate the process design, plant operations procedures and the control
scheme configuration.
GENTRY:
We are currently adding caustic in front of the biological treatment tanks in order to offset
the decrease in pH created by the biological activity process. Sources of the caustic include those
created as byproducts from the refinery processes and also fresh caustic is required. We do have
an inline pH monitor to provide continuous feedback for control.
RASBOLD:
Our Tulsa refinery drains caustic from a breakout tank, which has captured rinses from a
propane KOH (potassium hydroxide) caustic scrubber. This material is not directly drained to the
bio unit, but is slowly drained into the sewer system at a drainage rate to prevent any final
effluent permit exceedences from our waste water unit. Our sulfide concentration in the effluent
is typically in the 0.02 ppm range while our daily maximum according to our discharge limit is
0.6 ppm.
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1998 TOC
On a more general note concerning pH control at our wastewater plant, we have an acid
tank and a caustic tank located at the headworks. These are tied into a pH probe, which
automatically controls our influent pH between 8.5 and 9.0. In addition, we have two pH probes
before the bio unit and two pH probes after. While typically not required, we can use these
probes to manually control the pH at these places as well.
ZETLMEISL:
Once alerted to the problem, make sure you take steps to protect the bacteria health and
population. If possible, the contaminated stream should be segregated and sent to a storage tank
where it can be injected into the total wastewater influent at a controlled rate. Either reduce or
eliminate bio wasting by going into total recycle of the activated sludge. Depending on the
biological health of the bio population, bio augmentation with specially adapted bacteria has
been shown to offer accelerated biodegradation rates. Monitor key performance indicators like
food/mass ratio, dissolved oxygen levels, pH, trace nutrients like phosphorus and nitrogen. You
also have to be prepared to separate the additional solids generated by using additional organic
coagulants or flocculants during final clarification. Finally, you might need to add an antifoam,
potentially in the aeration basin(s) and the final outfall.
CHRIS SPURRELL (Chevron Products Company):

Another problem if you have a sour water oxidizer is osmotic shock. The same thing
would happen if you had a neutralized caustic that has chlorides in it. The increased sodium level
can turn the little bugs into raisins or balloons when you turn it on or turn it off.
Question 20.
What microbiological control programs are available for cooling water
treatment and what are their effects on other treatment programs?
ZETLMEISL:
The two types of chemicals commonly used for microbiological control in industrial
cooling water systems are oxidizing and non-oxidizing biocides. Oxidizing biocides are typically
used as the primary microbiological control agent and non-oxidizing biocides are used as
supplements. Primary oxidizing biocides include: chlorine, bromine and chlorine dioxide.
Chlorine can be in either a gas, liquid (sodium hypochlorite solution), or solid (granular or tablet)
form. Bromine is available in either a solid or liquid form. Chlorine and bromine may also be
combined in a single product. Chlorine dioxide is a gas and must be generated on site.
At normal use concentrations (0.2-0.5 ppm free available oxidant) found in refinery
cooling water programs, they have minimal effect on most treatment chemicals, with two
exceptions. They are phosphonates, used for calcium carbonate scale control, and yellow metal
(admiralty brass, copper, etc.) corrosion inhibitors, which are various types of triazoles.
Some commonly used phosphonates can be reverted to ortho phosphate by oxidizers. If a
high degree of reversion occurs, normally the result of free available halogen concentrations in
excess of 1.0 ppm, the system could be left with less effective calcium carbonate scale control.
This scale control is extremely important in elevated pH programs where scaling potential is
greatest. The amount of reversion is dependent on the type of phosphonate and the type and
concentration of oxidizing biocide used.
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At Baker Petrolite we have a phosphonate that is very oxidizer tolerant, i.e., with
reversion rates of less than 10%. As mentioned, the yellow metal corrosion inhibitors, which are
triazoles, are also affected by oxidizing biocides. The most cost effective method to compensate
for this oxidation is to slightly increase the azole feedrate. This method ensures system
protection and is far less costly than utilizing more halogen stable alternatives.
The other type of chemicals are non-oxidizing biocides like alkyl dimethy benzyl
ammonium chloride, dibromo nitrilopropionamide, glutaraldehyde, and 5-chloro-2-methyl-4-
isothiazolin-3-one . Non-oxidizing biocides are generally compatible with most water treatment
chemicals, although care must be taken in product selection to ensure against charge
neutralization of the dispersant package.
SMITH:
At Valero, we use a continuous chlorine with a “chlorine helper” type product, a strong
detergent which is non-phosphate. This will not suffice when a process leak is affecting the
recirculating water. This is just a microbiological normal operating maintenance program.
Damage control for process leaks can vary but have one common factor. “They are very
expensive”. If microbiological control gets out of hand, then we use a non-oxidizing biocide like
a quatinary amine.
TRAEGER:
I am going to comment a little bit on non-oxidizers. We just recently converted our
cooling towers from gaseous chlorine to non-oxidizing scenario. The main driving force was
relative to storage of the chlorine. Generally, non-oxidizers are in the range of three to five times
more expensive than the chlorine. Small quantities of the non-oxidizer are generally required.
You must alternate the non-oxidizers that are utilized to avoid developing resistant
biopopulations. There is the potential of sterilization of downstream biotreatment systems. As
Mr. Zetlmeisl said, non-oxidizers generally do not degrade copper corrosion inhibitors or
dispersant polymers.
The biocides we are using our glutaraldehyde, DBNPA, and a blend of quaternary amines.
The corrosion inhibitor program that we are using is a molibdate phosphate program. We have
completed about one summer with the non-oxidizing biocides. We have lowered iron levels in
the cooling tower while still maintaining high cycles. We have not seen any impact at this time
on the waste water treatment facility that receives these cooling tower blowdown streams. The
costs of the program are coming out in the four to five times range of the cost that we spent on
chlorine.
MASTRACCI:
Two of our refining facilities use liquid chlorine for the majority of the biological control
in cooling water systems. Occasionally, proprietary, non-oxidizing biocides are used to cope
with short term hydrocarbon leaks to the system. These hydrolyze at a pH greater than 7.5 and
cause little or no adverse effect on the waste water treater biological system.
Question 21.
What is the future of MTBE on the basis of potential groundwater
contamination? How will refiners blend reformulated gasoline it MTBE is
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banned?
WALDRON:
The world seems to be looking for a way to eliminate, minimize or replace MTBE as
improved remediation measures are researched. The fact that this quest continues verifies the
difficulty of problem. MTBE has excellent fuel properties. Therefore, alternatives remain elusive
for various reasons. Whatever the solution to the problem may be, a high priority should be to
encourage Congress to eliminate the two percent oxygenate mandate for RFG from the Clean Air
Act. The oxygenate mandate in RFG is unjustified. It makes no environmental sense to mandate
oxygenate content as it is only one of seven gasoline properties monitored to certify RFG
emissions utilizing the EPA complex model.
Elimination of the mandate would enable use of MTBE to be reduced as the search for a
suitable replacement is progressed. It is important to understand the problem as alternatives for
MTBE are explored. MTBE has a low odor and taste threshold and is very soluble in water.
Hence, any spilled gasoline will pose a greater remediation problem if it contains MTBE.
Unfortunately, all ethers have the same characteristics with regard to odor, taste and
miscibility with water. Ethanol is the obvious candidate in the alcohol family. However, ethanol
aggravates VOC emissions. Other alcohols are also being considered, but they tend to be very
toxic. An update on this issue is expected at the end of the year when a report by the California
Energy Commission is expected.
TURPIN:
The future use of MTBE and its impact on groundwater contamination will not be
decided on the merits of technical arguments. I see the MTBE battle being a big political battle
fought between the environmentalists, the water recreation enthusiasts and special interest groups
such as the agricultural community. This last summer, the use of jet skis on California lakes was
limited to certain days of the week because of MTBE contamination. “Joe Surfing Dude” let the
environmentalists run up the cost of gasoline a few cents, but he is not going to stand for anyone
taking away his toys. With the huge grain surplus that we now have, the backlash I think will
come against all ethers, (after all, if one either is bad they all are in a political argument). The
strong agricultural lobby has been pushing ethanol for years. I think refiners are going to be
forced into blending with only ethanol in some geographic areas.
JACKSON:
The U.S. EPA remains solidly behind the use of MTBE as a component of reformulated
gasoline. The problem of groundwater contamination is being addressed by targeting leaking
underground storage tanks. Final regulations become effective at the end of 1998. The U.S. EPA
has refused so far to grant any additional extensions for bringing these storage tanks into
compliance with the new regulations.
Question 22.
In cooling water service, we are concerned with the performance of critical
exchangers operating at low flows and high water temperatures. What can we
do to minimize corrosion and fouling in this service?
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LAMB:
I do not think that there is a universal solution for cooling water problems on critical
services. I would encourage people to look for the cause of the problem. One of the first places
to look is at the cooling tower circulation pumps to see if there is additional room on the pump
curve. If the pump is operating way down on the curve, maybe you can look at cutting back on
some non-critical services and making more cooling water and hydraulic capacity available for
the critical services.
Also, you need to look at hydraulics at the service. Identify where the largest pressure
drop is and the greatest opportunity to correct the flow problem. The hydraulics versus design is
a good think to look at normally. On a short-term basis, to correct an operating problem, you
may want to look at redundant services that can be isolated so you can do some chemical
cleaning onstream. On surface condensers, you can do some temporary piping to divert exhaust
steam from the surface condenser to the atmosphere so you can either mechanically clean or
chemically clean the heat exchanger.
For the longer term, additional cooling water pumps, changing the number of tube passes
on the heat exchanger service may make sense. In addition, you can work with your cooling
water vendor to see what they can do to help you out by improving water quality. Maybe a
complete cooling water survey to see what modifications can be done to the whole system to
improve the system’s long term operation is in order.
TURPIN:
I have experienced these concerns in the past when a few key water-cooled exchangers
were located on elevated decks. The cooling water pumps were pumping sufficient water, but we
just could not get water to the upper decks. We fought the problem with back flushing, air-
burping, on-line cleaning, Oke-coolers, mini-shut-downs, installing backpressure valves etc., all
resulting with no real satisfactory operation. We ended up putting a couple of in-line pumps in
the supply water lines going up the structures. This not only provided the water we need up the
structures, but it also allowed us to open some of the back pressure valves we had installed and
created a greater water flow through the entire cooling system. Because we only needed 30-40
feet of head, the drivers were very small. Although we added a continuous electric cost for the
drivers, our net costs were reduced when maintenance and improved yields were considered.
WALDRON:
I agree with what has been said. At above 130°F, the phosphate chemical tends to start breaking
down. Without a doubt, hydraulic surveys of the cooling water systems are typically always
beneficial.
Solid & Chemical Waste
Question 23.
What documentation is required by refiners' policies covering spent
catalyst disposal and metals recovery? Are refiners auditing spent
catalyst processors? Do the certificates of recycle/destruction being
offered by the spent catalyst processing industry limit the refiner’s
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environmental liability? How do you handle and document spent

ceramic catalyst support media?
ALLEN:
I would like to thank CRIMET for their input into the answer this question. I have split it
up into the sections outlined in the question.
Documentation Required:
All US refiners are required to manifest the shipping and disposal of hazardous wastes.
Currently, characteristically hazardous spent catalysts (e.g. benzene and/or arsenic containing
catalysts or those exhibiting self-heating or reactive characteristics) must be reported on a
“Uniform Hazardous Waste Manifest” to the State where ultimate disposal or recycling of the
spent material will take place. Non-hazardous spent catalysts may now be shipped under a bill-
of-lading, without any further manifests. Effective February 1999, all spent hydrotreating and
hydrorefining catalysts will be listed as hazardous, regardless of characteristics. Starting then, all
these spent materials may require a manifest. Additionally, a Land Disposal Restriction or
“LDR” or “Land Ban” form must be issued with each hazardous or listed spent catalyst shipment.
Prudent waste management practices by the refiner include keeping proper documentation
of all manifests, bills-of-lading and Land Disposal Restriction forms, together with all analytical
data supporting the selection of the hazardous waste codes and underlying constituents of the
waste. Additionally proper maintenance of all Department of Transport (DOT) shipping
documents, which require accurate description of wastes being shipped, as well as correct coding
and labeling of shipping containers, is essential.
Auditing Spent Catalyst Processors:

Most refiners especially the majors, routinely audit spent catalyst processors.
Recycle/Destruction Certificates : Limiting the refiner’s environmental liability:

Certificates of recycle provide waste generators with a paper trail of their responsible and
sound waste-management practices. CRIMET is not aware of any regulation under current U.S.
law which provides protection to the waste generator (with or without a recycle certificate) from
environmental liability should the processor’s site become a Superfund site.
Handling and Documenting spent ceramic catalyst support media:

In the case of our affiliate, CRIMET, ceramic supports are separated from the spent
catalysts prior to the introduction of the spent catalysts to the metals manufacturing process. They
are washed and sent out to third party processors for further cleaning and resale. Ceramic
supports are exempt from the upcoming listing rules.
SMITH:
Concerning documentation required by refiners' policies covering spent catalyst disposal
and metals recovery, prior to the EPA's recent listing of hydrotreating catalysts as hazardous
waste, our catalysts have rarely been found to be hazardous. This being the case, documentation
has followed the requirements for non-hazardous waste in the State of Texas. After the new
listing take affect in February 1999, we will have to change our procedures. If we are able to
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exempt recycled catalysts from hazardous waste regulation as substitutes for metal ores we will
document the material like any other product. Documentation will include catalyst metals
content, price agreements and bills of lading. If the catalyst is managed as a hazardous waste, we
will document on site inspections, waste evaluation information, disposal facility approvals and
retain copies of hazardous waste manifest and land ban restriction forms.
In response to the second part of the question, Valero audits spent catalyst recyclers and
disposal facilities every three years.
Regarding the certificates of recycle/destruction limiting the refiner's environmental
liability, the certificates of recycled/destruction do not in themselves offer any liability limit.
However, recycle and destruction do offer less liability than disposal.
Finally on the last part of the question, Valero has recovered ceramic support material
from some catalysts in the past for reuse. However, because our catalysts have typically been
non-hazardous, economics were found to be poor. With the new EPA hazardous waste listing of
hydrotreating catalysts, we plan to reevaluate this practice. We know we will not be able to
recover support material from our largest catalyst waste stream, which is our resid hydrotreating
catalyst, because it cannot be easily screened.
TRAEGER:
For material that we know is hazardous, we utilize hazardous waste manifest system as
our only means of documentation for the movement of spent catalyst for disposal or metals
recovery.
The only audits that we have performed have been for those processors that are
recovering precious metals. We do accept certificates of destruction when provided or certificates
of recycle, but we agree that they do not provide the refinery any reduction in liability.
Recently, a facility to which we ship non-hazardous Claus unit catalysts was shut down
by the EPA. We were forced to go to the facility to determine which material was ours, remove
it. Even though we had certificates of destruction from this facility, the facility had been simply
warehousing our material.
On the issue of support material, generally support material mixed with hazardous
material is not separated in our facility and we ship it out to a certified facility to be dealt with.
Some support material that is separated from non-hazardous catalyst we do reuse in our
operation.
Question 24.
In an ongoing effort to reduce overall wastes, we are investigating the
possibility of recovering ceramic support media from our spent catalyst prior to
processing at the catalyst recycling facility. Theoretically, this practice should
reduce the overall volume to be processed, and associated costs. Have other
refineries recovered and recycled this product?
MASTRACCI:
In general, we do not consider it to be economical to screen catalyst which has been
dumped from a reactor. The catalyst bed size is usually very large relative to the volume of
ceramic support media. The decision to screen the inert balls for re-use should be based on the
cost of screening on-site versus the cost of transporting the total load to a reclaimer or
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1998 TOC
regenerator and returning the inerts for re-use. We do not believe that attempting to separate the
inerts by vacuuming them from large catalyst beds will be worthwhile. We conducted a detailed
study on a hydrocracker with a little more than 200 mlbs of catalyst and found it to be
uneconomic to attempt to screen the catalyst at our Corpus Christi site.
Our New Jersey facility has found it advantageous to recover and reuse inerts from a 30
mlb catalyst charge. The break point will likely differ for each location and should be analyzed
on a case-by-case basis.
As a note, we have successfully used inerts from brokers who recycle these materials
from various sources.
SMITH:
I agree with what has been covered. We have had support media cleaned and returned to
the refinery and kept it in storage.
RANDALL D. LOFLAND (Catalyst Trading Company, Ltd.):

Many refineries are currently recovering and reconditioning spent support media. In some
instances, the routing of spent inerts are dictated to the catalyst processing facility by the refinery.
Other refiners have cut out shipments of spent inerts to processing facilities altogether, opting to
deal directly with support media recyclers. This method minimizes handling, reduces catalyst
processing costs and represents a variety of logistical and administrative advantages for
everyone.
Question 25.
How do you dispose of the packaging of chemicals and catalyst shipped in
nonreturnable containers? Can it be recycled? Have any of the catalyst
manufacturers considered switching to a returnable and reusable catalyst
packaging system?
BENNETT:
The answer to the question starts with the fact that the non returnable containers such as
bags and super sacks usually end up in state or EPA approved landfills. Drums have previously
been reconditioned. As a provider of both liquid and solid products, we have started to provide
liquid products in recyclable cycle drums. These are containers either owned by the customer or
ourselves and are “cycled” between the customer and UOP when a refill is required.
We generally supply all our catalyst products in drums or super sacks. Drums definitely
seem to meet the criteria of reusable and recyclable, but they do not seem to be a part of today's
recycle loop at the present time. In the past there were reconditioning facilities available for
those materials.
We occasionally deliver products in catalyst flow bins and we expect the use of those
containers to increase dramatically in the future.
GENTRY:
To follow up on previous comments, the drums, whether they are plastic or metal, that we
receive, into the refinery are not recycled. They are generally triple rinsed and disposed of in
industrial landfills. Super sacks are also cleaned out and disposed of in industrial landfills. We
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1998 TOC
have continued to work with catalyst manufacturers to develop the capability to supply the fresh
catalyst in a reusable or returnable system. Within the next few months, we are going to try our
first round of having hydrotreating catalysts supplied in reusable flow bins.
ALLEN:
Over the past ten years refiners have moved to a recognized system for packaging of
spent catalyst in returnable and reusable catalyst bins. Presulfurized hydrotreating catalyst is
typically packaged in returnable catalyst bins such as those provided by Federal Container.
Fresh hydrotreating and hydrocracking catalyst is currently delivered in non-returnable
bulk bags, bins or drums. The bags are typically destroyed in the loading process, instead of
taking the time to open the bag, usually the bottom of the bag is slit with a knife. In fact Criterion
have been experimenting with re-useable bags under strictly controlled conditions on internal
plant-to-plant shipments. The bags can be used many times if handled correctly, however even
under these conditions the bags get damaged. We are aware of a company that is developing a
returnable catalyst packaging system. Practically speaking though, such a new system would have
to have the blessing of both the catalyst manufacturers and the Refiners. As always with have to
be a cost-effective solution. Right now most catalyst manufacturing plants are ill-equipped to
handle bags. Returning bags adds to the catalyst vendors costs – I do not think that the industry
would be prepared to share in this.
For spent catalysts shipped in drums, our affiliate CRIMET empties, cleans and crushes
steel drums and disposes of them to a scrap metal company. Pallets, tarps and other packaging
material are disposed of in an industrial landfill.
TRAEGER:
In a lot of cases, for the chemicals we utilize, the liquid chemicals in the refinery, we have
gone to porta-feed systems that are either reloaded on site or returned to the original supplier
when empty. In the case of fresh catalyst drums, we do reuse a lot of the catalyst drums for
various uses throughout the refinery. We get a couple, two, three go rounds on them and then
they are cleaned and crushed and disposed of in state approved industrial landfills.
RON FUNK (Federal Container Canada Ltd.):

Over the past decade, spent catalyst packaging has evolved from single-trip, non-
returnable options, i.e., drums, bags and pallets to Intermediate Bulk Containers (IBC’s) also
known as Catalyst-Bins. This reusable packaging system eliminated the waste associated with
more historical methods and contributes to the following economic and environmental benefits:
i) Large container size means less manpower is required.

ii) Refinery sites and catalyst processing facilities are no longer cluttered with catalyst
packaging waste.
iii) Waste tonnage sent to landfill has been significantly reduced.
iv) Movement of these containers can be tracked with sophisticated inventory control
systems, thereby reducing the chance of losing product or containers.
1) Service providers offer Catalyst-Bins on a rental basis. Refineries, catalyst
processors and catalyst handling companies no longer need to be concerned with
purchasing, storing and maintaining their own containers.
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Until now, fresh catalyst has been typically packaged and shipped in non-returnable,
single trip containers, i.e., bags and/or drums and pallets. Secure confinement for high value
catalysts and environmental concerns are only two issues that are raising the profile of fresh
catalyst packaging. Our reusable, returnable system incorporates a durable Intermediate Bulk
Container. A detailed tracking system records the location, ship date and return date of each
container providing closure at the completion of every job. Hundreds, even thousands of throw-
away bags, drums and pallets no longer end up in the landfill reducing overall waste and the costs
associated with disposal.
C. Energy Management
Question 26.
Has anyone had success with dual firing (fuel oil/fuel gas) of low NOx
burners? We continually need to repair and replace burners due to heat
deterioration of the metal parts and coking of gas tips. If yes, who is the
manufacturer of the burners and how are the burners typically operated –
several burners in just oil service, some firing all fuel gas or all burners
firing part gas/part oil?
TRAEGER:
Unlike many refiners, we still do burn liquid fuel in our refinery. In some cases, we have
dual fired with fuel gas. However, we have not duel fired low NOx design burners. Relative to
the issue of the tip problem, our fuel system can range from straight FCC clarified oil to as much
as 50% PDA derived pitch. Coking and deterioration can be a problem for these fuel oil tips,
especially as fuel viscosity is increased. Generally speaking, maintaining the viscosity of the fuel
oil to the burner tip at or below about 15 centistokes by adjusting the temperature of the
circulating fuel oil loop has resulted in good performance of these fuel tips for us.
I did speak to one manufacturer who does design and sell air stage dual fired low NOx
burners. This company is Zeeco, Inc. Their air stage design can burn just fuel or a combination of
fuel oil and fuel gas. Generally for combined operation, where they fire oil and gas, they would
fire all burners in that service in dual service.
ALLEN:
The feedback I have had from our friends and partners in Syn Technolgies at Fluor Daniel
is that they have not heard of any successful commercial applications. However one of the burner
manufacturers has recommended that one way round this problem would be to segregate the type of
fuel burned in each individual burner. One of the fuels could be used to base load the duty and the
total firing of the heater adjusted with the other feed. Typically the fuel gas is used to adjust the total
firing.
BENNETT:
Coking of the burner tips in these type burners could in fact be related to the burner tip
placement relative to the burner tile. If the burner tip was inserted too high up in the tile, it could
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1998 TOC
result in coke build up on the oil tip and oil dripping down due to loss of the primary air velocity
across the tip. If the tip is too low in the tile, the flame will impinge on the tile on the exit. This
will then cause sooting of the edges of the outlet and coke buildup on the tile, oil splashing, oil
spills and coking of the gas tip.
I agree with Mr. Traeger on the viscosity and you also want to take a look at the oil
pressure and steam pressure differential. We think the steam pressure should be at least 30
pounds above the oil pressure.
We also do not think that you should fire both fuels in the same burner at the same time.
This is partly because the gas tips will foul unevenly over time and the gas flame burns faster
than the oil flame, so it can tend to rob the air from the oil flame.
Regarding temperature control, you want to base load with one fuel and temperature
control with another. If you do dual fire, we expect that the overall flame lengths will be longer
by 20-50%.
JAMES D. WEITH (Fluor Daniel, Inc.):

Mr. Traeger, were you filtering the slurry oil? What kind of particulates did you have in
the slurry oil (part per million)?
TRAEGER:
Part per million, I cannot answer you. We generally run about a .2 to .3 BS&W on our
clarified stream. We do not have any separation on that stream.
ROGER WITTE (John Zink Company):

I agree with the panelists in regard to the control of the fuel on the gas and baseload the
other one. The oil temperature and the steam differential is very important. The tolerances and
the positioning of the oil tip, tile and the gas tip is very important to ensure good combustion.
Probably the most important thing on low NOx type burners is the control of the air through three
separate dampers and the air distribution inside of the pea box is very important. We have found
that in some applications that if air distribution is poor, it will cause coking on the gas tips and
problems with burning the fuel oil.
ASHUTOSH GARG (Furnace Improvements):

Fuel oil and fuel gas have been successfully fired using staged air burners in a number of
installations. These burners are essentially low NOx oil burners with the fuel gas firing capability
built into them. The air staging works better with oil but it does reduce NOx with fuel gas. A lot
depends upon how this burners are operated as staged air burners have three air registers per
burner and it is normally very difficult to adjust all the three dampers in a multiple burner
furnace.
The other type of burner that has been used in this service is the ultra low NOx burner,
which comes with flue gas internal recirculation. These burners are essentially gas burners and
reduce NOx based on fuel staging and flue gas recirculation. Sometimes an oil gun is installed in
the center to fire oil. Typically these burners used to have a metal bluff body where the primary
fuel gas firing would take place. In some cases these bluffs started getting deformed after a
period of 3-4 years. Since these burners are still being developed the burner companies have
come out with models that have tangential firing of primary gas tips and even the metal body has
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1998 TOC
been reduced to a cylinder. These burners have been in service for at least 3-4 years and no
problems have been reported.
Good operation of the burners is very important in ensuring long life of these burners. It
is recommended that all the burners should be fired whenever possible. If the burners are
shutdown a little airflow will help cool the internals in the burners. The best ways to fire
combination fuels in a heater is to base load one of the fuels (mostly gas) and supplement it with
the other fuel (generally oil). The best performance of the burners will be achieved if all the
burners are fired uniformly. There is no way to control combustion airflow in individual burners
if some burners are fired on gas and other on oil. This is because there is no way to know how
much excess air should be fed to the burners firing gas and to the burners firing oil. It may lead to
sub-stoichiometric combustion in some burners and super stoichimetric combustion in the other
burners. Shutdown some of the burners at the turndown if they are not needed.
Good Ultra Low NOx gas and oil burners are made by Callidus Technologies and John
Zink Company in US, by Air Oil (now a part of Peabody group) in UK and LD Duicker in the
Netherlands. Our recommendation would be to use staged air oil burners for combination firing.
We also recommend that you test the burner at the vendors test facility before you buy and install
them in the heater. Burner specifications also play a great part in the performance of burners.
Correct sizing and specification of the burners is also very important. Furnace Improvements has
been helping a number of clients in sizing, specifying burners correctly and also witnessing the
burner tests.
Question 27.
What has been the panel's experience with regard to pigging of heater coils?
How does it compare with steam air decoking?
MASTRACCI:
Steam/air decoking of course will burn off any carbon or hydrocarbon found in the heater
coils. Any non-combustible solids, which are small and loose may be carried away by the steam
and nitrogen. However, gas velocities may not be high enough to carry away any metal scale
adhered to the inner wall of the coil. Pigging is intended to solve this problem. By passing pigs
sized for the inside diameter of the coils, any remaining metal scale should be removed.
We have used the pigging procedure at 3 of our 4 refineries. The procedure was quite
successful, and in one application, mechanical damage did not allow steam/air decoking to be
used. Pigging was the only option. We had one case on a coker heater where we successfully
pigged 2 of 4 passes. As it turns out, we may have ended the pigging procedure prematurely on
the other 2.
Some practical advise. Whether you steam/air decoke or pig, the heater tubes must be
inspected for damage like bulges - by strapping or other method, residual coke, that is ringing the
tubes and any other routine turnaround inspection normally done. If not, you run the risk of
restarting with a potential problem still in the heater.
RADCLIFFE:
I have a couple of examples of use of the pigging technique. PCK in Germany used
pigging to clean their vacuum visbreaker, high severity visbreaker furnaces. The vacuum furnace
was the first where this technique was applied in 1994. As a result, they observed lower off gas
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temperature and a 1.8% improvement in fuel efficiency.

The Visbreaker furnace is cleaned every 18 months. Cleaning the four pass furnace takes
about 18 hours. Similarly, the two pass high severity visbreaker takes about 18 hours. The
pigging procedures takes about one day less than the steam air decoke and results in less stress to
the furnace tubes.
The cost of the procedure has dropped significantly since they first started using it.
While I was at Milford Haven, we switched from steam air decokes to pigging for the
vacuum furnace in 1992. Again, this proved to be extremely successful. We had never really
successfully got a good burn on the steam air decokes we had previously attempted.
We saved about one day going from about five days to four days, and we solved one of
the major problems we had with steam air decokes namely noise complaints from neighbors.
Also, the gas flows for the furnace were dropped by about 2% after the decoke.
The other thing that was interesting for us is that we were able to determine the location
of most of the coke. The predominant amount of coke was in the roof tubes of the cabin furnace,
as a result of flame impingement. The most heavily coked passes were the third and fourth out of
five. The overall cost is almost certainly lower if increased tube life, reduced interference with
the turnaround schedules due to live utilities, and fuel costs are taken into account.
RASBOLD:
At our Tulsa refinery, we pigged two crude unit vacuum heaters for the first time during
our March 1998 turnaround. One heater is four pass while the second heater is two pass. We
compared the heat transfer rate in the heaters once they were online after the pigging. These rates
were very similar to those results after a typical steam air decoking process. Inspection of the
tubes yielded no significant loss from potential metal scoring from the pigs. One of our
incentives of pigging the furnaces in Tulsa was that the process was essentially a turnkey
operation from our supplier, with very little Sun operator or engineer involvement during the
process itself. With steam air decoking, monitoring of the process required one engineer and one
operator during the entire event. Pigging these heaters allowed Sun personnel to concentrate on
other turnaround activities. Our largest incentive to pigging these heaters was timing. Heater
work for our turnaround was one of the critical paths. Pigging of both heaters took 36 and 24
hours respectively, as compared to over 96 hours total for the steam air decoking.
Our Yabucoa refineries have had similar experiences with a crude vacuum heater. We
reduced decoking time there from five days for steam air decoking to two days with pigging and
had almost identical recovered heat transfer coefficients for both processes.
As far as pigging furnaces in different types of operating units, we have also pigged a two
pass coker charge heater in our Tulsa refinery. We typically steam air decoke this furnace and
will continue to do so due to the furnace needing to be decoked every six months. However,
during one operating cycle, we severely coked the tubes and were unable to get enough flow
through the furnace for a steam/air decoke. So we hydroblasted one pass and pigged the second
pass. Once complete, we steam air decoked the entire furnace as a proof burn. The amount of
proof burn between the two passes was insignificant in either case.
Finally, as a side comment concerning an experience we had pigging our Philadelphia
refinery crude unit heater. We pigged one pass only to remove scale. During subsequent
inspection of the outlet headers for unrelated naphthenic acid corrosion, pigs were found in
several locations within the header after the pigging process had already been completed.
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Needless to say, accurate inventory of the pigs being utilized by the supplier must be done.
SMITH:
At Valero in Corpus Christi, we have pigged both our HDS heater and our vacuum
furnace with very good success. We used a Canadian company (Pinnacle Pigging Systems, Inc.,
Red Deer, Alberta). I believe the last one we did cost approximately $30,000. No additional
thinning of the U-bends were noticed afterwards. We do a thorough inspection after we pig. The
advantages of pigging have been stated as; any restrictions will be found, reduction in pipe
damage, improved safety, cost effectiveness, significant reduction in shutdown time and
environmental friendly.
TRAEGER:
We have seen similar experiences. We have done one heater with the pigging procedure.
One other advantage I would mention is that while the pigging procedure is going on, you can go
into the heater and perform other maintenance such as burner repair and things of that nature.
I have a couple of minor problems that we did run into that I will mention. On the outlet
radiant key fitting or the last two in the radiant section, we missed the fact that its internal shape
was oblong instead of round. The result was that we tore up a whole bunch of pigs that we had
not intended to tear up. But we did get through the heater and got it clean.
The second thing we ran into is this heater has key fittings on both ends of the tubes. We
went through great efforts to make sure that before we told the contractor he was finished and
could leave, that it was clean, and checked that there were not any pieces of coke left. However,
after startup, we plugged some feed nozzles on the riser to the FCCU. I think what was going on
was the non-uniformed shapes on the key fittings were holding some small pieces of coke that
did not get moved out of the system until we got up to full charge rates.
The other final area of discussion in regards to pigging has to do with non-uniform or
deformed tubes. There has been some discussion in industry that the pigging process is unable to
remove coke from buldged sections of tubes, for example. The result could be localized higher
tube wall temperatures because of the failure to remove the coke in that section. Some of the
different pigging contractors claim to be able to utilize varying degrees of over sized pigs to
address this problem and should be considered when you are looking at decoking a heater.
ASHUTOSH GARG (Furnace Improvements):

Based on the feedback received from our clients, the results are mixed. Some clients have
had very good experience with pigging but others are not happy. It appears that the pigging
process is still improving and is yet to reach maturity. At the same time, due to infrared
thermography becoming more and more common and affordable, steam air decoking is also
gaining ground.
In the pigging process, the client needs to do a little homework before the pigging process
can start. The coke in the tubes needs to be estimated to determine the initial pig specifications.
The coke thickness in the tubes is not uniform and also the coke thermal conductivity varies
widely anywhere from 1.2 to 30 btu/hr ft2. If the coke thickness is overestimated the price of
pigging as well as time required goes up. On the other hand if it is underestimated, there is a
chance of pig getting stuck in the tube. If the pig is stuck in the tube then the process of locating
pig, cutting the tube and putting a new piece back is a very long and time consuming affair. It is a
47
1998 TOC
good idea to do a field survey of the heater and then do heater modeling to estimate the coke
thickness. This can save a lot of hassles and time. Furnace Improvements has estimated coke
thickness prior to pigging for several clients.
If the coke deposits are of normal thickness like 3 or 2 inches and the provision of steam
air decoking is already existing in the plant, steam air decoking often turns out to be more
economical. Use of infrared thermography can cut down the time by monitoring the tube
temperatures and hot spots, if any. The time required by steam air decoking is generally longer
than pigging. It is normally not controlling most of the time.
Pigging is useful and economical if the coke layers are thicker than 2 inches as steam air
decoking will take a much longer time to burn out the coke inside the tubes. Pigging is also faster
and does not pollute the atmosphere. Pigging can be a problem if heater tubes have plug headers
on one side or both sides of tubes. Some clients have reported that the pigging was not able to
remove coke completely and some saw scorching of tubes inside surface. A number of
companies are coming out now with inspection instruments which can check the tube inner
surface very accurately and ensure that the tubes are completely cleaned.
Question 28.
What determines a safe contingency capacity for plant utility systems?
TURPIN:
Generally speaking, we consider a safe contingency capacity for a utility to be that
quantity of the utility needed for operations to: 1) determine that a disruption has occurred, 2) the
magnitude of the disruption, 3) the actions needed to bring the plant into a “Safe” condition, and,
4) then to bring the plant into that “safe” condition.
The plant utility systems that can have a capacity are the plant instrument air system and
the instrument electrical system. Other utilities such as the fuel, steam, boiler feed water and
hydrogen systems typically have an alternate operation such as a propane vaporizer for the fuel
system.
Instrument air systems are normally designed with about a 30 minute contingency
capacity. This is supplemented with air bottles on critical valves that are sized with sufficient air
to cycle the valves 4 or 5 times. It is quite common to also have nitrogen supplies linked to
instrument air system for emergency use after the contingency air supply is exhausted. This
introduces several safety issues that are beyond the scope of this question but need to be
reviewed prior to connecting a nitrogen system to an air system.
UPS and battery back-up systems are typically installed for instrument electrical systems.
Sizing varies depending upon their use, but a couple of general rules of thumb are; instruments
20-30 minutes, DCS 30 minutes and APC computers 60 minutes.
If the four operating actions listed above can not be accomplished on a processing unit
within these default time frames, contingency capacities should be enlarged as needed.
TRAEGER:
I guess as process superintendent, if I had triple redundant utility systems, I would be
happy. But I do not have that.
In terms of electricity, we utilize UPS systems for all of our DCS control systems and
emergency shutdown devices in the field. In terms of the electrical power supply to the refinery,
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1998 TOC
our potential connected load is actually much higher than the electrical power we can supply. We
have laid out the system such that the loss of any individual transformer or motor control center
generally will affect all the process units in the refinery, but not have a severe effect on them. So
that has been our approach from the electrical standpoint.
In terms of steam supply in the refinery, we have been through all the various drivers,
anything that is critical in terms of a power failure such as reflux to a column all have a steam
driver associated with them.
Throughout the refinery, we operate about five individual boilers. The capacity of the five
boilers put together is about 300,000 pounds an hour. Typical summer steam requirements are
140,000 pounds per hour, and typical winter requirements are about 250,000 pounds per hour.
Steam demand during any sort of an extended power failure in the summer or winter can far
exceed our steam capacity and require some careful triage to keep the pressure up on the steam
system.
We operate a single instrument air compressor and dryer that is electrically driven. The
load on the compressor generally is about 90 percent of design capacity for that machine. We do
have a spare diesel driven instrument air compressor. As Mr. Turpin mentioned, we also have
plant air cut ins and nitrogen cut ins to support the instrument air pressure.
GARY HILL (Lion Oil Company):

I have a two-part question. The first part is, would the panel comment on the
effectiveness of an external steam ring on a process heater as a line of defense against a flashback
fire that might occur as a fuel source line rupture or a blown pump seal.
The second part is, has anyone done any calculations on the dilution effect of the steam
on the fuel air mixture that will be drawn into the fire box and would you please comment on
your findings?
RADCLIFFE:
At Milford, we did use a number of steam rings on critical service pump seals, hot oil
pump seals, also on certain critical flanges where we had had experiences of flange leaks and
fires. Generally speaking, these were not operated continuously. They were there as a means of
dispersion and control of any fire pending extinguishing the fire.
We had no real problems. They worked quit well when we did have problems with leaks.
I would agree with Mr. Turpin. I think one of the things you need to look at perhaps is
when you changed burners whether you may have had a change in the heat flux through the front
side of the tube. I suspect that when you changed to a low NOx burner, which generally have a
taller flame, that may have had an effect on your heat flux.
GARY HILL (Lion Oil Company):

One of our safety personnel was wondering if anybody has done any calculations to
indicate what the dilution effects of activating the steamring on the fuel. It will be drawn into the
firebox since the firebox is still running. It is under negative pressure.
TRAEGER:
We have looked at that same issue and unfortunately we do not have a good answer. We
have talked about setting up some mechanisms to initiate snuffing steam or filling the firebox
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1998 TOC
with steam. Then at some time interval shortly thereafter we would close the damper to convert it
to a positive draft situation and tying all that in to fuel shutdowns. We have not implemented that
on any heaters yet.
ROGER WITTE (John Zink Company):

The question is how much steam do you think is going to be drawn into the furnace?
Some steam going in and the water from the combustion reaction is very good. It would help
tremendously. But it is a very inefficient way to inject the steam. I do not think that you would
get enough steam in if you put a steam ring around the furnace to hinder the combustion process
whatsoever.
WALEED SALAMAH (Saudi Aramco):

Recently, we changed our crude unit heater burners to low NOx, SOx and noise type
burners. After about ten months of operation, we experienced severe oxidation of tube externals
which led to two tube leaks. We never experienced this oxidation before. Also, we found a very
thick coke formation inside those tubes, reaching in some areas about 15 millimeters.
During the operation, there was no recognized flame impingement on the tubes or
changes in the heater duty. Even the flame shape was much better than with the previous burners.
The second part of my question is that for such heaters during an emergency shutdown,
we noted several occasions where the tubes go out from the retainers and the holders, even
though we have high pressure steam to the coils that are supposed to hold the tube and keep it in
place.
We have dual fuel, very heavy fuel oil and fuel gas.
TURPIN:
It sounds like the flame pattern was significantly changed and thus the heat distribution in
the firebox was changed with the new burners. Your comment that “the flame shape was much
better than with the previous burners” further advances this theory. Did you by chance also
change the fuel at the same time?

No, the fuel was the same.
TURPIN:
My guess is you did something incorrect in the burner installation, or possibly the wrong
burners were specified for the dimensions of your firebox. You probably need to get back to the
burner manufacturer and find out exactly what has created localized hotter spot in that box. I
have seen a couple of installations where similar problems were noted and the causes were the
burner tips were installed in the wrong location of the throat and in other cases the burner tips
were the wrong size. There could also be some operating problems such as incorrect air
allocation (the low NOx burners typically have tertiary registers that are very difficult to adjust),
low/high oil pressure, low/high oil viscosity and low/high dispersion steam pressure. On those
tubes where you saw the additional coking, they probably had higher tube metal temperatures in
that particular area.
Regarding your comment about the tubes coming out of the hangers during an emergency
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1998 TOC
shutdown, this problems is probably also related to the same issue of heat distribution in the
firebox. The steam flow is not providing an adequate heat sink to remove heat from the tubes.
You may want to check your emergency procedures, including recalculating the steam rate.
MASTRACCI:
I would agree with Mr. Turpin. I think one of the things you need to look at perhaps is
when you changed burners whether you may have had a change in the heat flux through the front
side of the tube. I suspect that when you changed to a low NOx burner, which generally have a
taller flame, that may have had an effect on your heat flux.
RADCLIFFE:
One question I would ask is, was the external oxidation even? Or was it in certain tube
passes or in patches on individual passes?

Actually, I found it in almost all the passes of the heater, but it was concentrated only in
the bottom tubes.
TURPIN:
This really sounds like the heat flux has been changed in the lower tubes in the firebox.
You need to go back to the burner manufacturer and get recommendations from them.
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1998 TOC

ROBERT L. HORAN (MPR Services, Inc.):

JOHN SORIA (Hci Coastal Chemical, Houston, Texas):

TOM BACON (DOW Chemical Company):

DAVID BURNS (Union Carbide Corporation):

treated a 10 percent slipstream of the circulating amine.

ROBERT ALLEN LANNING (KTI Fish):

ARTHUR W. DEZEEUW (Koch-Glitsch Field Service):

of the contactor can reduce these losses by an order of magnitude.

JOHN DIBBLE (Aminetech, Inc.):

MODESTO ORTIZ (MPR Services, Inc.):

JAMES LEWIS (TPA, Inc.):

PATRICIA FORERO (Merichem Company):

JAMES JENKINS (Huntsman Corporation):

TOM BACON (DOW Chemical Company):

DUKE TUNNELL (Amine Best Practices Group):

KENNETH G. TASKER (IFP North America):

ERIK STEWART (The Dow Chemical Company):

DAVID BURNS (Union Carbide Corporation):

TOM BACON (DOW Chemical Company):

DUKE TUNNELL (Amine Best Practices Group):

JAMES D. WEITH (Fluor Daniel, Inc.):

TOM BACON (DOW Chemical Company):

Equivalent Concentration Maximum Recommended Concentration

DAVID BURNS (Union Carbide Corporation):

TOM BACON (DOW Chemical Company):

TOFIK KHANMAMEDOV (The Tofik K. Khanmamedov Company):

DAVID BURNS (Union Carbide Corporation):

(hence pressure drop).

JAMES LEWIS (TPA, Inc.):

RAGHU MENON (BOC):

STEVE FENDERSON (Goar, Allison & Associates, Inc.):

ASHA MASOHAN (Indian Institute of Petroleum):

ROBERT BEST (Air Products and Chemicals Inc.):

SRU Capacity Increase With Oxygen

• Excessive temperatures in the reaction furnace combined with unsuitable

compositions and turndown ratios.

JOHN BOURDON (Black & Veatch Pritchard, Inc.):

RAGHU MENON (BOC):

STEVEN FENDERSON (Goar, Allison & Associates, Inc.):

JOHN BOURDON (Black & Veatch Pritchard, Inc.):

STEVEN FENDERSON (Goar, Allison & Associates, Inc.):

ROBERT BEST (Air Products and Chemicals Inc.):

Turnaround Sulfur Recovery Unit

Burner Reaction WHB

• Amine Acid Gas

JAMES LEWIS (TPA, Inc.):

STEVEN FENDERSON (Goar, Allison & Associates, Inc.):

PAUL VANCE (Acreon Catalysts):

ASHA MASOHAN (Indian Institute of Petroleum):

STEVEN FENDERSON (Goar, Allison & Associates, Inc.):

JAMES LEWIS (TPA, Inc.):

Tail Gas Plants

STEVEN FENDERSON (Goar, Allison & Associates, Inc.):

ASHA MASOHAN (Indian Institute of Petroleum):

HUGO BILILONI (Biopari, Argentina):

JOHN BOURDON (Black & Veatch Pritchard, Inc.):

Responding Question 13, Brimstone Engineering out of either Denver, Colorado or

adopted partly as an effort to reduce overtime expenses in maintaining the instruments.

JIM ABBOTT (Synetix):

low temperature shift.

samplers under GGG.

•Shift in pH from acid or caustic type materials.

CHRIS SPURRELL (Chevron Products Company):