Annual Meeting

March 19-21, 2017

Marriott Rivercenter
San Antonio, TX

AM-17-27 Prepare, Produce, Profit: Debottlenecking

Refineries through Comprehensive Feedstock
Preparation

Presented By:

Austin Schneider
Crystaphase
Houston, TX

Patrick Gause
Crystaphase
Houston, TX

American Fuel & Petrochemical Manufacturers 1667 K Street, NW 202.457.0480 voice

Suite 700 202.457.0486 fax
Washington, DC www.afpm.org
20006.3896
This paper has been reproduced for the author or authors as a courtesy by the American Fuel &
Petrochemical Manufacturers. Publication of this paper does not signify that the contents
necessarily reflect the opinions of the AFPM, its officers, directors, members, or staff. Requests
for authorization to quote or use the contents should be addressed directly to the author(s).
Prepare, Produce, Profit: Debottlenecking refineries through
comprehensive feedstock preparation
What are the obstacles limiting your planned cycle lengths and turn around schedules?
Alternatively, what are the impediments to simply regaining control of your cycle and
running your most valuable assets the way you need to? What are the impacts of
modified turnaround schedules to your refinery throughput? Shutdowns result in skims,
catalyst replacement, and poorly performing equipment and are among the costliest
events in a refinery. Taking these assets out of service limits throughput of upstream
processing units, and results in significant opportunity losses. The ability to avoid these
costly events ultimately comes down to defining and understanding feedstock
contaminants and identifying the bottlenecks in your facility. Combining the capabilities
of Baker Hughes and Crystaphase® addresses these obstacles. With tools to plan and
execute holistic strategies, refiners mitigate bad actors on multiple fronts. This In turn
greatly increases reliability, availability, and cycle length.

Commercially advantaged crudes offer improved profitability, but at the cost of a wide
array of particles and poisons that can quickly erase any expected windfall if not
adequately addressed. Additional contaminants are generated throughout the
processing train, from initial distillation to sulfur recovery. It is well known that these
contaminants can constrain throughput in distillation and desalting operations and, if not
dealt with properly, can further impact downstream hydrotreating operations.

Provided in the remainder of this discussion are strategies to deal with inherent and in-
situ contaminants throughout the refinery. Following the path of the feedstock through
the refinery, the authors demonstrate the benefits of complementary approaches to
managing the particles and poisons that can limit refinery profitability.

Desalter Optimization

In the refinery, the desalter is often regarded as the first and only line of defense to
remove particles, poisons, and soluble contaminants. In the desalting process, fresh
wash water is mixed with the incoming crude so that it can contact entrained salts,
solids, and other contaminants. When the desalter is upset, the amount of these solid
and particulate contaminants released to the crude unit can increase significantly. For
this reason, the desalter is often the focus of attention when unexpected and
unacceptable levels of contaminants carry downstream with the desalted crude.

Maximizing contaminant removal in the desalting process requires attention to optimizing

the wash water rates, temperature, mixing, level and chemical demulsifier choice and
dosage. However, operating outside of design conditions or with process limitations can
result in inadequate desalting performance. In such cases, refiners are faced with few
options and often must limit the types of crude oils processed, foregoing profit
opportunities. Baker Hughes has developed a method called Crude Oil Management™
approach that looks beyond the desalting operation and takes a more comprehensive
view of all equipment, processes, and feedstocks that ultimately contribute to reliable
desalter operations 1. The program features a suite of tools including engineering

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practices, monitoring tools, and a variety of chemical treatments to provide a targeted
and effective solution to the problem at its actual source while minimizing negative
downstream impacts.

One tool that has been applied successfully to improve desalter efficiency in many
refineries is crude oil pretreatment. Crude oil pretreatment is a strategy to relocate
demulsifier injection from the desalter to the crude storage tank in order to significantly
increase the contact time of the demulsifier with the crude oil. It allows time for the
demulsifier to penetrate through the crude oil to treat surfaces and interfaces. When
pretreated crude oil is charged to the unit and enters the desalter, it is poised for quick
and efficient emulsion resolution and release of solids to the brine. In addition,
pretreatment breaks up emulsions in crude tank bottoms and minimizes sludge release
from the tankage. It stabilizes the quality of the crude feedstock, allowing the desalter to
operate at higher mixing pressures and maximize salt and contaminant removal.

A proper pretreatment program reduces the amount of demulsifier applied at the desalter
in direct proportion to the amount injected into the crude storage tank. Pretreatment
programs, therefore, often result in a net decrease in chemical spend. Pretreatment
demulsifiers are engineered for low-temperature functionality in the tank farm, and, in
addition to demulsification properties, they should be designed to condition solids for
partitioning into the desalter brine.

One US Gulf Coast refiner was running a heavy crude (API 16-18) and experiencing
frequent desalter upsets. The desalter emulsion interface was difficult to control and
often in excess of 5 feet. The brine contained significant amounts of oil, resulting in
excessive slop oil generation. A pretreatment program was applied at the tank farm
using the XERICTM heavy oil demulsifier program. Within 24 hours of initiating the
pretreatment program, the desalter emulsion layer was reduced from 5 feet to less than
18 inches. Oil in the brine leaving the desalter was reduced to <500 ppm, and the refiner
was actually able to increase the amount of heavy Canadian Crude in the feed from
approximately 10% to over 30%. Significantly, the pretreatment program provided
reliable desalter operation which allowed an increase in the mixing energy. This, in turn,
resulted in an increase in salt removal efficiency from approximately 88% to 94%.
(Figure 1). This translated to significantly fewer contaminants and catalyst poisons being
charged to the crude unit.

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 Figure 1. Improvement in salt removal with optimized mix valve DP.

Another Crude Oil Management tool that has been applied successfully to improve
desalter efficiency is the JETTISONTM solids release agent (SRA)2. The SRA conditions
solids in the crude oil to facilitate their partitioning into the desalter brine, where they
drop out and are removed from the bottom of the vessel. In a successful SRA program,
a significant amount of solids are removed from the crude oil and transferred to the brine.
The effluent brine is dirty with solids, but these solids are oil-free.

In one US Gulf Coast refinery, heavy crude oil was being processed with high levels of
solids. These particles promoted emulsion interface growth in the desalter and poor brine
quality. Removal of the solids from the crude was inefficient, ultimately causing fouling
of downstream equipment. An SRA treatment program was developed and initiated.
Immediate benefits were seen as the emulsion layer was reduced by 35% and solids
loading was shifted to the lowest trylines (Figure 2). Solids removal efficiency across the
desalter (desalted crude vs raw crude) was improved to more than 70%. This actually
allowed the refiner the ability to increase the solids-laden opportunity crude to
approximately 50% of the total charge, resulting in $135,000/day incremental profit while
minimizing negative downstream impact.

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 Figure 2. Solids release to bottom of desalter with JETTISON program.

Metallic contaminants in crude oil can influence the desalter operations and, if allowed to
continue past the desalter, can affect downstream catalyst performance. Two particular
metals of prominence are sodium (Na) and calcium (Ca). While routinely present as
chloride salts, these metals can also exist as salts of naphthenic acids. When improperly
treated and carried over with emulsions, these naphthenate salts can also impact
downstream operations and catalysts.

Removal of naphthenate salts is a critical objective if a refiner wishes to process

opportunity crudes. Desalter acidification offers an approach to converting the metals
into water soluble salts that are easily removed with the desalter brine. This not only
removes the metals from the desalted crude, it improves desalter operation and reliability
by converting the naphthenates into oil soluble naphthenic acids. These acids must be
accounted for downstream in both a corrosion program and in the impact these corrosive
components could have on hydrotreater fouling.

The solution offered by Baker Hughes to provide safe, cost effective desalter acidification
is its EXCALIBUR™ contaminant removal technology3. The EXCALIBUR product line
features acids selected to achieve metals removal targets while avoiding the major
downstream impacts of commodity acids.

A European refiner was attempting to process a deeply discounted African crude high in
calcium naphthenates. The crude blend, containing up to 20% of the African crude,
contained calcium levels as high as 119 ppm. Desalting performance when processing
the crude oil was unacceptable, limiting the amount of crude in the crude blend. Baker
Hughes recommended a desalter acidification program using the EXCALIBUR

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technology. The treatment program achieved an average calcium removal of more than
75% (Figure 3) while at the same time meeting the required salt removal and crude
dehydration targets and providing improved waste water treatment operation.

Calcium Removal with EXCALIBUR Treatment

100 100.0
90 90.0
Calcium Content (wppm)

80 80.0
70 70.0
60 60.0
50 50.0
40 40.0
30 30.0
20 20.0
10 10.0
0 -
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Analytical Data Set

Raw Crude Desalted Crude % Removal Average Calcium Removal

Figure 3. Calcium removal program.

Corrosion Byproduct Removal

While many of the constituents and contaminants in crude oil are directly responsible for
harming catalyst bed operation, some of the concerns arise from a secondary impact.
Three examples of crude contaminants that fit this description are the feedstock
presence of tramp amines, the presence of naphthenic acids, and the presence of sulfur.
All three of these can produce conditions of high corrosion in the process units. The
byproducts of the corrosion (iron salts) can contribute to reactor bed plugging and
hydraulic limitations. The corrosion mechanisms involved differ for these three
contaminants, as do the locations where the metal loss will occur; however, the impact to
reactor bed is the same.

Tramp amines can enter the crude distillation unit in the crude oil, in refinery slops
streams, and via the desalter wash water4. Regardless of the source, these amines
create stable emulsions and react with hydrolyzed HCl, producing corrosive salts that
liberate iron from equipment surfaces. The released iron salts can, in turn, carry to
distillate hydrotreating beds and contribute to hydraulic limitations. Tramp amines,
consequently, represent a dual threat to reliability and operation of refinery processes,
including fixed bed catalysts. Mitigating these tramp amines can be achieved by proper
management of desalter pH. Baker Hughes EXCALIBUR™ contaminant removal
technology provides a means to reduce desalter pH, which, in addition to improving salt

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removal efficiency, causes tramp amines to partition to the desalter brine, reducing the
potential for overhead system corrosion.

A gulf coast US refinery processed a topped crude that was treated to mitigate H2S. The
scavenger chemistry used in the crude produced a byproduct tramp amine,
monoethanolamine (MEA), which reacts aggressively to form HCl salts. Tower top
corrosion was severe, leading to operational limitations and increased maintenance to
repair corrosion damage, all while generating corrosion products that foul downstream
reactor beds. A multi-step mitigation program was implemented to reduce overhead HCl
concentration and EXCALIBUR treatment to bring desalter pH under control and reduce
overhead MEA concentration. Figure 4 shows the corrosion risk, reflected as the salt
approach temperature at the tower top before and with mitigation. The salt approach,
shown as MEA Salt Point ΔT (in °F), indicates high risk of corrosion as the value
approaches and goes below 0°F. Best Practice guidelines call for a target of +25°F to
minimize risk of tower corrosion. Figure 5A and 5B show the tower internals for
operation without and with the mitigation strategy. Minimizing the corrosion in the
upstream distillation process reduced the secondary impact of downstream reactor bed
fouling.

Figure 4. Mitigating amine salt corrosion in crude distillation tower.

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 Figure 5A. Tray condition without mitigation. Figure 5B. Tray condition with mitigation.

Complementing a robust corrosion mitigation strategy focused on minimizing the

generation of iron sulfide and other corrosion byproducts is a Crystaphase particle
filtration system immediately upstream of the catalyst bed. Crystaphase designs filtration
systems which will remove particles before the catalyst bed while minimizing pressure
drop build.

Illustrated in Figure 6 is an example of iron fouling where pressure drop was neither an
issue nor an indicator. Instead, this Gulf Coast refiner was experiencing catalyst
deactivation within six weeks of startup. This is a costly problem, as the catalyst in
question was made from platinum.

The refiner originally planned to perform a hot-hydrogen strip, then reactivate the catalyst
to run for additional 13-month cycles. However, when it came time for the strip, they
discovered iron deposits binding with and killing the catalyst. Instead of reactivating, they
had to vacuum out the reactor, haul the material to a metal reclaimer to separate the iron
from the poisoned catalyst, then install a new catalyst load.

Crystaphase recommended adding filtration to the catalyst bed in order to remove the
iron from the feed, mitigating the loss of activity and enabling regeneration of the
catalyst. At the next scheduled changeout—and for the first time since the unit had been
in operation—the refiner found no iron deposits and was able to regenerate the catalyst.
This operational change saved the refinery $3,000 per day in lost catalyst and operating
capability.

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 Figure 6. Reformer catalyst before and after Cystaphase CatTrap filtration system installed.

Corrosion in higher temperature zones can lead to the same secondary impact of fouling
at reactor beds. As temperatures increase, amine-HCl salt corrosion ceases to be a
concern. In its place, corrosion due to naphthenic acids and sulfur compounds results in
release of iron that will flow downstream and deposit in reactor beds. Naphthenic acids
are high molecular weight carboxylic acids that have been shown to corrode tower
internals, piping, drums, and heat transfer equipment at temperatures as low as 400°F.
The iron liberated from this corrosion mechanism will be soluble iron naphthenate, which
flows downstream and will react spontaneously in the reactor to form iron sulfide. Like
naphthenic acids, sulfur compounds can also corrode refining equipment at high
temperatures, producing iron sulfide scale that can foul reactor beds. Crude oils high in
TAN and high in sulfur are frequently discounted compared to benchmark crudes. For
both naphthenic acid and sulfur corrosion concerns, profitability can be limited when
feedstock limits on TAN and sulfur are required.

Mitigating against high temperature corrosion while processing high TAN or high sulfur
crudes can be accomplished in the long term by capital investment to upgrade
metallurgies to corrosion-resistant alloys. In the short term, high temperature corrosion
inhibitors have proven to be a reliable means to manage operation while processing
these attractively priced crude oils. Baker Hughes SMARTGUARD™ high temperature
corrosion control program offers a suite of corrosion inhibitors and application monitoring
capabilities that control high temperature corrosion and unlock the refinery’s profit
potential. An inhibitor program application shows a clear benefit by reducing corrosion
rates by more than 80%, as shown in Figure 7. Reactor pressure drop benefits from
high temperature inhibitor treatments were also demonstrated (Figure 8), as the
reduction in corrosion products achieved by controlling corrosion resulted in a lower rate
of pressure drop increase in the reactor beds.

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 Gas Oil Corrosion Activity vs. Inhibitor Dosage
Corrosion Activity (H2 Flux) 300 60

250 50

200 40

Corrosion Inhibitor Dosage (vppm)

150 30

100 20

50 10

0 0
0 50 100 150 200 250 300
Days on Stream

Corrosion Activity Inhibitor Dosage

Figure 7. High temperature corrosion inhibitor provides > 80% reduction in metal loss.

Gas Oil Hydrotreater Reactor Bed Pressure Drop

70

60

50

40
∆P (psig)

30

20

10

0
0 20 40 60 80 100 120 140

With Corrosion Inhibitor No Chemical

Figure 8. Pressure drop trend data.

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In a characteristic example, one gulf coast refiner had experienced pressure drop issues
for years. A filtration system installed above the main catalyst bed had little effect, and
the reactor was unable to go beyond a 24-month production cycle. Pressure drop limited
cycle time to as little as six months.

Crystaphase identified the offending problem as a high TAN, iron naphthenates issue
with the ability to evade capture until precipitation as iron sulfide in the catalyst bed. Iron
naphthenates are formed in situ by the following mechanism7:

Reaction 1. Corrosion of iron by organic acids, likely occurring on the walls of upstream piping
and equipment

2ܴ‫ܪܥ‬ଶ ‫ ܪܱܱܥ‬+ ‫ ݁ܨ‬଴ → (ܴ‫ܪܥ‬ଶ ‫ ݁ܨ)ܱܱܥ‬+ ‫ܪ‬ଶ

2ܴ‫ܪܥ‬ଶ ‫ ܪܱܱܥ‬+ ‫ܪܥܴ( → ݁ܨ‬ଶ ‫)ܱܱܥ‬ଶ ‫ ݁ܨ‬+ 2‫ܪ‬

Reaction 2. Thermal decomposition of acid salts

(ܴ‫ܪܥ‬ଶ ‫)ܱܱܥ‬ଶ ‫ܪܥܴ → ݁ܨ‬ଶ ‫ܪܥܱܥ‬ଶ ܴ + ‫ ܱ݁ܨ‬+ ‫ܱܥ‬ଶ

Reaction 3. Iron oxide reacts with organic sulfur or hydrogen sulfide (H2S)

‫ ܱ݁ܨ‬+ ܴᇱ − ܵ − ܴ → ‫ ܵ݁ܨ‬+ ܴᇱ − ܱ − ܴ

‫ ܱ݁ܨ‬+ ‫ܪ‬ଶ ܵ → ‫ ܵ݁ܨ‬+ ‫ܪ‬ଶ ܱ

Scanning electron microscopy (SEM) confirmed the precipitation problem, as shown in

Figure 9.

Installing a system employing ActiPhase® and CatTrap® technologies enabled the unit to
achieve a 20-month production cycle with no increase in pressure drop (Figure 10). The
improved cycle lengths have resulted in a profitability increase of over $25,000 per day.

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 Figure 9. Precipitated iron sulfide generated from iron naphthenates.

Figure 10. CFHT processing high-TAN VGO feed stock. Crystaphase increased cycles more than threefold following
sample analysis and optimization.

Utilizing these tools to control and address corrosion issues, large increases in cycle
lengths can be realized. Simultaneously mitigating the source of the foulant, controlling
the size of the particles, and optimizing the filtration for the prepared feedstock removes
costly bottlenecks and shutdowns. By leveraging the advantages of these approaches,
refiners are free to work with catalyst vendors to drive their cycle lengths with activity
design. In this way, feedstock preparation can increase profitability on the order of
millions of dollars per year.

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Fouling Mitigation

When addressing hydraulic limitations (or pressure drop issues), a number of variables
come into play when identifying the root cause of the problem. The most common is
particle deposition in the catalyst bed, which is not something catalyst is designed to
handle well. Additionally, there are special cases where this particle accrual can occur
upstream of the reactor, wreaking havoc on the thermal and hydraulic efficiency of heat
exchangers and furnaces alike. Most polymerization products react in this portion of the
reactor and tend either to require shutdown due to hydraulic limitation in the heater or
exchanger, or to build to catastrophic levels. At this point, flow conditions or processing
conditions cause a sloughing event, dumping copious quantities of particles directly into
the upstream reactor, moving the hydraulic problem from the heating train into the
reactor bed. Even the most advanced filtration solutions can have trouble dealing with
these situations.

An engineer might look at this problem in two different ways, either as a particle
infiltration problem to be solved with particle removal, or as an antifoulant problem to be
solved with chemicals and additives. Both options should be examined in parallel so the
designed systems and programs complement one another to reach targeted run lengths.

Antifoulant treatment programs will inhibit the formation, growth, and deposition of
offending materials in refinery processes. Fouling control programs reduce the rate of
fouling in refinery operating systems. LIFESPAN™ fouling control additives include
surfactants that disperse organic and inorganic particulates, and polymerization inhibitors
that reduce formation of high molecular weight polymers and gums. Dispersant and
asphaltene stabilizer antifoulants reduce agglomeration and particle size growth to keep
the particles suspended in the process stream. Polymerization inhibitors act to terminate
free radical or condensation polymerization reactions, thereby reducing formation of
insoluble organic particulates. These programs may consist of multiple additives which
are selected based on the deposition mechanism(s) contributing to the problem.

LIFESPAN antifoulant programs have been highly successful in controlling fouling in

hydrotreating units, not only preheat exchangers, but also in guard beds and reactor
beds.5 In hydrotreating units, deposits are typically composed of inorganics, such as iron
sulfide, and polymerized organic particles formed of reactive species in the feed. When
fouling control programs are used, the ability of CatTrap technology to remove poisons
and dissolved impurities is enhanced because the particles are restricted from growing
beyond the capability of reactor filtration systems. In one refinery study at a naphtha
hydrotreating unit, the particle size of iron sulfide was measured at three locations of the
feed system, as shown in Figure 11. By controlling the particle size in a predictable way,
filtration systems can be optimized to match the expected behavior.

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 Figure 11. Effects of LIFESPAN antifoulant program to control particle growth of iron species.

A distillate hydrotreating unit at a major integrated refinery was experiencing rapid fouling
in the feed-effluent exchangers and guard bed. Analyses of the various feeds being
processed revealed the major problem was a light coker gas oil (LCGO) coming to the
unit via a blanketed intermediate storage tank. A LIFESPAN fouling control program was
implemented after a unit shut down for cleaning. A polymer inhibitor was injected into
the hot LCGO prior to the intermediate storage tank and a dispersant antifoulant was
injected into the combined feed to the unit to control inorganic and organic particle
growth. Fouling of the unit effectively ceased once the treatment program commenced.
Figure 12 shows flow corrected pressure drop across the guard bed before and with
treatment to control the rate of deposition.

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 Figure 12. Guard bed pressure drop - distillate hydro-desulfurization unit fouling

Different feedstocks present different challenges. In another case involving a cracked

naphtha feedstock, the challenges had become so severe that cycle lengths had become
limited to 93 and 74 days before engineers began work with Crystaphase to design a
filtration system for the vessel. Prior to Crystaphase, this unit was using a standardized
system of medallions, macroporous lobes, and ring grading, a system which was ill-
suited to the feedstock it was facing.

Crystaphase was able to assess the problems facing the unit and develop a cycle-
extending solution for the refiner. The results are depicted in Figure 13. The initial
installation quadrupled the cycle, reaching 320 days on oil before shutdown. Gathering
valuable samples from the unit, Crystaphase was able to determine an additional
component in the fouling process, polymer breakthrough, which was bypassing the
CatTrap system and then reacting and accumulating on the catalyst bed. Crystaphase
corrected this issue by implementing a complete filtration system using a combination of
CatTrap and ActiPhase DOS, enabling the capture of reactive polymerization products
prior to deposition of the catalyst bed. Typical carbonaceous materials found in these
filtration systems are shown in Figure14. This solution further enhanced the
Crystaphase filtration system, enabling a cycle of over 500 days. Further optimizations
to this system have been pursued and installed to meet a cycle requirement of 24
months. Table 1 depicts the enhanced capture of carbon and polymer conversion
ActiPhase solutions are able to offer. Furthermore, a dispersing program such as
LIFESPAN has been recommended to the refiner to keep the heat exchangers and
CatTrap/ActiPhase system performing in top condition. The combined profitability impact
on the hydrotreater alone is over $10,000 per day.

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Figure13. NHT processing cracked Naphtha Feed stock. Crystaphase increased cycles nearly eightfold following
sample analysis and optimization.

Figure14. Carbonaceous fouling extracted from cracked naphtha process.

Table 1. Improved carbon capture rate from implementing active filtration systems.

CatTrap Only ActiPhase DOS

Carbon Wt % 5.1 55.5

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There are many refiners today dealing with high fouling rates and incredibly large
particles due to polymerization in the heating train. By developing a plan with experts in
feedstock preparation, it is possible to develop complementary solutions which will
greatly enhance the fouling resistance of hydrotreaters. Simultaneously improving heat
exchanger and furnace performance, controlling the size of the organic foulants, and
proactively employing active filtration will minimize upsets, skims, and opportunity losses.
This clears the path of all obstacles to cycle length except catalytic activity, which allows
the refiner to plan for improved profitability.

Poison Control

This same synergy can also be demonstrated in the ability to deal with poisons. As an
exemplary case, we will review silicon’s role and the best plan of attack to deal with that
poison.

When dealing with activity limitations on the catalyst bed there are many detrimental
contributors to this problem. These poisons tend to show up predominantly as soluble
components of the feedstock. Poisons can be defined as chemical species with a strong
gradient for chemical adsorption or absorption on catalyst sites, blocking this valuable
resource for use in the desired chemistry of the vessel. In large part, the poison
depends on the catalyst being used, the pressure and temperature of the vessel, and the
preferred chemical reaction taking place. In the case of hydrotreating, sulfur and
nitrogen species react with the hydrogen present and are released from the oil as
ammonia or hydrogen sulfide. While the hydrotreating catalyst performs exceedingly
well at this conversion, it also performs nefariously well at poison collection. Poisons in
these cases are numerous, but can include components like silicon (from antifoam
siloxanes), organometallics (nickel and vanadium species), metalloids (arsenic species),
and even reactive, carbonaceous materials. If these poisons are allowed to reach the
catalyst bed, accelerated reductions in catalyst reactivity are experienced and short
cycles ensue.

The most common hydroprocessing poison in naphtha hydrotreating is silicone, typically

quantified as wt% of elemental silicon on the catalyst. Though naturally occurring in
many crudes, the primary source of silicone is poly-dimethyl siloxane (PDMS) additives
used to control foam formation in coking operations. While vital to good coker
operations, these compounds present a serious threat to hydrotreater catalysts. Once
broken down, the silicone polymers will readily attach and block active sites on the
catalyst, eventually threatening breakthrough to further impact reformer operations as
well.

Newly developed antifoams reduce the amount of silicon necessary to control foaming in
delayed coker operations, thereby reducing the rate of catalyst contamination in
hydrotreating units. The industry has been gradually changing from shorter chain-length
PDMS to higher molecular weight molecules. The higher molecular weight PDMS are
more thermally stable and provide longer lasting foam control which reduces antifoam
treatment rates. Table 2 shows the change in silicon concentration of the coker products
when a refinery changed from a 60,000 cSt PDMS product to a higher molecular weight,

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600,000 cSt product. On average, a 50% to 60% reduction in silicon contamination of
the coker products is found when upgrading to the higher viscosity PDMS.
Table 2. Silicon in cracked products – plant 1.

Naphtha LCGO HCGO

Si (ppm) using 60,000 cSt Antifoam 34.0 7.9 7.3
Si (ppm) using 600,000 cSt Antifoam 12.3 3.2 2.7
Si Reduction 59 % 59 % 63 %

Baker Hughes has developed the FOAMSTOP™Low Catalyst Impact (LCI) series of
products6 , which feature a modified siloxane molecule. These products control foaming
with less overall silicon, therefore contamination of coker products is substantially
reduced when compared to even the 600,000 cSt antifoam as shown in Table 3.
Table 3. Silicon in cracked products - plant 2.

Naphtha LCGO HCGO

Si (ppm) using 600,000 cSt Antifoam 33.8 28.7 1.8
Si (ppm) using FOAMSTOP LCI Antifoam 8.2 3.2 0.9
Si Reduction 75 % 88 % 50 %

These state of the art antifoam additives reduce the silicon loading of the cracked
products which must be hydrotreated before they can be blended to final on-road fuel.
Reduction of the overall concentration of silicon in the cracked products allows the
hydrotreater to operate longer before catalyst changes are required. When coupled with
Crystaphase MC Si silicon adsorbent, the reactor can run to its planned activity outage,
as opposed to being subject to early catalyst change-outs.

After solving pressure drop issues in naphtha hydrotreaters, the second most common
cycle limitation is silicon breakthrough requiring a full catalyst change and lost
throughput. To further extend that approach, Crystaphase has also built systems that
perform a simultaneous function of filtration and poison control using silicone-adsorbing
ActiPhase, as shown in

Table 4. By moving some poison capture into the filtration design, poison control depths
can be reduced and more flexibility can be provided to engineers and catalyst vendors to
reach other operational goals, such as improved LHSV and operational control.
Table 4. Capture of silicone in ActiPhase filtration systems and Crystaphase poison control.

CatTrap ActiPhase Si MC Si 2.5

Silicon Wt % 0.64 6.6 22.1

By using state of the art FOAMSTOP LCI antifoam products in concert with ActiPhase
high capacity silicone adsorbent, the impact of silicon on the hydrotreating catalyst is

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minimized. With this poison controlled, the refiner can now allocate more space to the
vessel’s primary function, nitrogen and sulfur removal.

Summary

The primary obstacles to turning around on schedule can be characterized in terms of

managing particles and poisons in hydrotreater feedstocks. Gaining control of cycle
lengths and maximizing the performance of valuable refinery assets is a matter of
dealing with these contaminants both inside and upstream of the reactor.

By implementing a chemical treatment program that anticipates support from a

complementary in-reactor purification system—and vice-versa—a refiner can amplify the
benefits of each. If suffering from hydraulic limitations, whether from organic or corrosion
foulant, consider not only options which protect the catalyst, but also chemical treatment
options supported by a complementary filtration system. If suffering from activity loss
due to poisons, make sure all options to reduce poisons upstream are considered while
also maximizing your ability to capture poisons before the hydrotreating catalyst.

With a feedstock properly prepared for nitrogen and sulfur removal, the refiner operates
assets on their designed timeline. A holistic approach to feedstock preparation entails
both the chemicals treatments and reactor purification systems. The resulting
performance improvement affects operations across the entire refinery, with the potential
to boost profitability by multiple factors.

Finally, it is critically important for refiners to coordinate strategies between their

suppliers in order to capture the maximum benefits of a multi-faceted solution. Applying
this concept and using the tools outlined in this paper can mitigate bottlenecks and allow
the refiner to prepare, produce, and profit.

References

1. S. Cornelius, D. Jackson, D. Longtin, ”Assault on Salt”, Hydrocarbon Engineering,

September, 2012
2. G. Hoffman and D. Longtin, “Innovation Leads to New Solids Management
Technology”, AFPM Annual Meeting AM-14-33, Orlando, FL, March 2014
3. J. Weers and J. Nguyen, “A New Metals Removal Process for Doba Crude Oil”,
ERTC 9th Annual Meeting, November, 2004
4. R. Rechtien and G. Duggan, “Identifying the Impacts of Amine Contamination on
Crude Units”, NACE Corrosion 2006, paper number 06581
5. B. Wright and G. Medine, “Distillate Hydrotreater Fouling”, Presented at AIChE
Spring Meeting, April, 2008
6. Proceedings from AFPM Q&A Transcript, Fall Q&A Meeting, October, 2016
7. U. Josh and A. Schneider, “Mitigating iron foulants in refinery processes”, ARTC
19th Annual Meeting, April, 2016

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