Distillate Hydrotreater Fouling

G. Medine, PhD
B. E. Wright, P.E.
Baker Petrolite Corporation
Sugar Land, TX

Prepared for presentation at the AIChE 2008 Spring National Meeting

Topical Conference on Refinery Processing (16a)

Session 9 Fouling Mitigation

April 9, 2008

Previously Unpublished
AIChE shall not be responsible for the statements or opinions contained in
papers or printed in its publications.

Copyright 2008 Baker Hughes Incorporated. All rights reserved.

Abstract
Fouling in hydrodesulfurization units is common throughout the refining industry. Hydrotreater
capacity utilization and asset availability can be reduced because of the sometimes significant
impacts of equipment fouling. Equipment fouling can result in inefficient heat transfer, rate
restrictions and equipment downtime. Hydrotreaters are prone to fouling at different stages of the
process and due to several different fouling mechanisms.
Low sulfur fuel regulations have resulted in higher severity operations of both naphtha and
distillate hydrotreaters. In addition, ever greater utilization and a need to run these units for
longer periods of time between turnarounds are common throughout the industry. As distillate
hydrotreaters (DHT) are being pushed to greater sulfur removal efficiencies, higher activity
catalysts and temperatures are being employed. These changes are resulting in an increased
incidence of fouling issues in distillate hydrotreaters. This paper will review the causes of fouling
in distillate hydrotreater units along with some of the possible solutions to these problems.
Introduction
During the past decade, fuel regulations have mandated ever decreasing amounts of sulfur. This
trend began with gasoline sulfur levels and has rapidly expanded to diesel fuel sulfur limits. The
allowable sulfur concentrations in diesel fuel are being stepped down over time based on rules
from the various regulating bodies. The Euro V standard specifies a limit of less than 10 ppm by
2009, and the US EPA has set a 15 ppm standard. Many other countries around the world are
adopting similar standards. As a result of these regulations, diesel hydrotreaters are being
revamped and run at significantly increased conversion rates, including increased pressures,
increased temperatures, improved high selectivity catalyst and increased throughput. Virtually all
distillate blending stocks must now be desulfurized including catalytically and thermally cracked
fluids, along with all straight run feeds, in order to attain the required sulfur concentration for the
overall pool.
As a result of the increased demand on hydrotreaters both in terms of throughput and sulfur
removal efficiency, an increase in problems and reliability issues have been seen around the
world. Fouling in the feed to effluent exchangers and reactor beds have increased, problems in
the furnace are becoming more common and hydraulic limits are being reached in some cases
well before the projected end of run. In addition, many refiners are processing low cost, and
lower quality, crude oils due to the price-advantage these crude oils have over premium crudes.
These opportunity crude oils usually contain higher quantities of sulfur and/or nitrogen
compounds compared to the premium crudes, or they contain significant quantities of naphthenic
acids, metals or salts which create numerous operating problems throughout the refinery
including issues at the hydrotreaters.
Distillate Hydrodesulfurization Units
A simplified distillate hydrotreater schematic is shown in Figure 1. The most significant
differences between distillate and naphtha hydrodesulfurization include operation at slightly
higher pressure and temperature, with much lower degrees of feed vaporization through the
preheat train and heater. In order to achieve increased sulfur removal efficiencies, refineries
have increased the severity of operation through the catalyst bed, including increased
temperatures, increased residence times and use of more active catalyst. Some plants have
added reactor beds in series in order to achieve the required level of sulfur removal. In cases
where an existing unit is being used to achieve significantly increased sulfur removal efficiency,
the residence time through the reactor must be increased and as a result, the throughput
decreases. This problem coupled with the need to process more of the overall distillate blending
stock has produced an increase in the numbers of distillate hydrotreaters operating at each plant
and a decrease in the available hydrogen supply. Overall, these factors have come together at
one time to yield a situation where diesel hydrotreater unit reliability, run length between
turnarounds and operational severity all need to be maximized.

Figure 1 Typical Hydrotreater Flow Diagram

Hydrogen Recycle Compressor
Makeup Hydrogen
Unit Charge

Feed-Effluent Exchangers
Feed Drum
Heater
Tank

Reactor
Separator Drum

Locations Prone to Fouling

In distillate hydrotreaters, fouling is most common in the feed side of the feed / effluent
exchangers. Fouling problems can also be observed in the heater, although this is usually a
result of poor flame patterns, the reactor bed, and the compressor.
Types of Fouling Common to Distillate HDS Units
Fouling deposits in distillate HDS units can be inorganic or organic in nature. Fouling can be
caused by the deposition of particulate matter (inorganic or organic) and the polymerization of
unstable molecules. The predominant fouling material in distillate HDS units is organic. The
source of inorganic fouling is usually iron sulfide, other corrosion products, catalyst particles or
inorganic salts entrained in the hydrotreater feed stream. Iron sulfide can be present as tramp
FeS carried from upstream units or as in situ FeS. For the latter scenario, iron that is dissolved in
the feed can react with sulfur in the feed or sulfide films on tube wall surfaces to form crystalline
growths that grow in place on hot metal surfaces. The particle size of in situ FeS is typically about
one micron near the inlet of the feed-effluent exchangers. At the outlet, the particle size can reach
about ten microns and eventually grow to several hundred microns at the inlet to the reactor bed.
Organic fouling in distillate HDS units results from the polymerization of unstable molecules in the
feed. Common fouling precursors include olefins, organic acids, mercaptans, ketones, aldehydes,
oxygen, organo-nitrogen compounds and organo-sulfur compounds. These compounds have the
potential to form polymers with themselves or upon reaction with other unstable compounds.
Oxygen promotes the polymerization of certain compounds, especially olefins. For this reason,
oxygen should be excluded from storage tanks of streams known to contain olefins. It is common
for feed components which are imported via ship, barge or pipeline to be contaminated with
oxygen. Some polymerization reactions can also take place in the absence of oxygen.
Metal ions, especially copper and iron can catalyze certain polymerization reactions. Metals may
be present in the feed if there is corrosion occurring upstream of the distillate HDS unit.
Two primary fouling mechanisms dominate polymerization in HDS feed streams: free radical
polymerization and condensation polymerization.

Free radical Polymerization

Free radical polymerization is a chain reaction that forms a long chain polymer (commonly
referred to as gums). Free radical formation begins with an initiation step that forms an initiator
radical. Typical initiators can be heat, oxygen, mercaptans and metals.

Figure 2

RH

Free Radical Polymerization: Initiation Step

Initiation
Initiator

Time

.
R

Initiator

Time

ROO.

ROOH

.
H

+
+

H.

Once an initiator radical is formed, polymers will start to grow as the initiator reacts on various
monomers; an olefin is an example of a typical HDS monomer.

Figure 3

Free Radical Polymerization: Propagation Step

Propagation

R.
.

ROO

R.

2
RH

ROO .
R . + ROOH
R-R

These polymers will continue to grow via additional propagation steps until a termination step is
reached that stops the growth of polymer. An efficient way to terminate this chain reaction is to
consume the free radicals, or their precursors, using special chemical additives.

Figure 4

R.

Free Radical Polymerization: Termination Step

Inefficient (not highly favorable)
R.

Termination
R-R

ROO .

R. +

ROOR
Efficient (more favorable)
Termination with Antifoulant

R.

AH

RH + A.

R.

A.

R-A

Condensation Polymerization
Condensation, or step reaction polymerization, is an example of a non-free radical
polymerization. It involves the combination of reactive compounds (ions rather than free radicals)
with other molecules to form a larger molecule with the loss of a simple molecule such as water.
This larger molecule can continue to react with other reactive compounds in the hydrocarbon
stream to make higher molecular weight polymers. Compounds like organic acids, carbonyls,
ketones or aldehydes, amines and pyrrole nitrogen will condense with each other to form larger
polymeric compounds. An example of this is the formation of amides.

Figure 5

Condensation Polymerization
Salt Formation

R-NH2 + HOOC-R
R-NH3+O2C-R-

R-NH3+O2C-RR-NHCO-R + H2O

The concentration of these species in distillate HDS feed determines how significant this form of
polymerization is to HDS fouling. Chemical additives are available which prevent this type of
polymerization. In some cases, the polymers that form in distillate HDS units are highly crosslinked or highly polar requiring special consideration in the development of an effective antifoulant
program.
The reactions discussed above all accelerate with increasing temperatures. Since the distillate
hydrotreaters are now being asked to remove ever increasing amounts of sulfur, many are being
run at higher temperatures and at full capacity. At the increased severity, the incidence of fouling
and reliability issues has increased significantly. The refinery should carefully consider the
strategy being employed when changing to ultra low sulfur distillate operation.
Identification of Fouling Precursors Root Cause Analysis
Baker Petrolite has developed a root cause analysis approach to identify the source of fouling,
the mechanism of fouling and solutions (both operational and chemical) to mitigate fouling.
Deposit Analyses
The first step in identifying the source of the fouling is to analyze the deposit that has formed in
the HDS unit. Primary areas of concern in distillate HDS that are susceptible to fouling include:
feed side of the feed/effluent exchangers, effluent side of the feed/effluent exchangers, heaters,
reactor catalyst beds and hydrogen recycle compressors. Analysis of the deposit reveals the
most information as to the source of the fouling problem. By using analytical techniques such as
XRF, XRD, TGA, FTIR and CHN analysis, it is possible to identify the material as inorganic or
organic in nature. These types of analyses can quantify inorganic salts, inorganic corrosion
products, or identify the functionality of the organic foulant that has contributed to the deposit.
Feedstock Analyses
Feed characterization is another important tool to help identify the mechanism that is causing the
fouling. A typical approach is to characterize the feeds analytically by a specific set of
compositional parameters known to indicate fouling potential. Fouling mechanisms are
determined by which parameters exceed concern levels.
Identification of the following compounds gives important information on the fouling mechanism
and the fouling potential of HDS feeds.
Organo-nitrogen and organo-sulfur containing
compounds can act as catalysts for free radical formation and for various condensation reactions.
Imines, an organo-nitrogen compound, are similar to carbonyl compounds except that the double
bond is between a carbon and a nitrogen atom instead of an oxygen atom. Because of this
similarity, imines can undergo condensation reactions resulting in a foulant that grows in
molecular weight resulting in gums or insoluble solids in the process stream. Enamines, another

organo-nitrogen compound, contain an olefin double bond and therefore can react as an olefin in
a free radical polymerization as well as undergoing a condensation reaction.
A bromine number test is sometimes run as a simple method to show whether olefins (excluding
aromatic olefins) and sulfur compounds reactive to bromine are present. Phenolics, sometimes
known as acid oils, tend to increase instability and increase peroxide formation in reactive feed
streams.
Mercaptans are acidic compounds. Mercaptans in the presence of oxygen or heat can form a
sulfidic radical (contains a free electron) that can initiate free radical polymerization reactions.
Mercaptans can also react with metals to form a complex that upon heating will also initiate a free
radical formation. Acid numbers are sometimes run to show the acidity of a feed stream. An
acidic environment tends to increase the reactivity of olefins and heterocyclics (containing
nitrogen, sulfur or oxygen) and accelerate conversion of peroxides to carbonyls.
Oxygen can promote polymerization of various unstable compounds, such as olefins. Therefore,
oxygen needs to be excluded from storage tanks, especially if the feed contains cracked, olefinic
feedstocks. Typically nitrogen blanketed storage tanks have been used but may be ineffective at
controlling fouling for feedstocks exposed to oxygen. This is because nitrogen cannot remove
oxygen reaction products like peroxide or hydroperoxides that may have already formed prior to
tankage. In addition, oxygen can mix with the feed causing fouling to accelerate in the feedeffluent exchangers if the seals in a transfer pump downstream of a blanketed tank are worn.
Carbonyl formation in hydrocarbons also can be a free radical reaction. An initiator radical can
act on oxygen to form an organic peroxide that decomposes to an alcohol radical and a hydroxide
radical. The alcohol radical can react with a paraffin molecule shifting the radical to the paraffin
and producing a carbonyl compound.
Fouling Tests
In addition to the deposit and feed characterization work, fouling tests can also be completed on
the feed streams to the distillate HDS units. Two common tests that are used are the existent
gums test and potential gums test. Modifications to these tests are essential as under normal
operating conditions distillate feed streams cannot be evaporated. Typically evaporation of these
samples requires superheated steam evaporation.
Existent gums are determined by evaporating light hydrocarbons from the field samples and
represent the amount of foulant inherent in the sample. The amount of gums (foulant) is reported
in units of mg/100 mL. High levels of existent gums typically require dispersant chemistries to
mitigate equipment fouling.
If the existent gums are low, then any additional foulant material that forms can be attributed to
reactions that occur during processing (in situ foulant formation). To investigate this phenomenon,
streams can stressed under various conditions and the resultant amount of foulant determined.
Foulant formed under stress of heat and nitrogen is referred to as thermal gums, foulant formed
under stress of both heat and air is referred to as potential gums and foulant under stress of both
heat and oxygen is referred to as oxidative gums. These parameters provide reliable indicators of
fouling potential.
Once the fouling potential and fouling mechanism have been identified via the root cause analysis
approach, the next step is to implement a cost-effective solution to mitigate the fouling. This can
be either an operational solution or a chemical solution or a combination of the two.
Fouling Control
There are several operational and fouling control additive program solutions that are available to
refiners to control distillate HDS unit heat exchanger fouling problems.

Operational Solutions
Various operational tactics can be used to help reduce fouling in distillate HDS units, including:

Inert gas blanketing of feedstock storage tanks

Notching the baffles in heat exchangers
Increasing the velocity of the feedstock through the exchanger trains
Installing feed filters to minimize the deposition potential of particulates
Blending protocols

Baker Petrolite recommends inert gas (for example nitrogen or natural gas) blanketing of storage
tanks especially for feedstocks that have been identified as having a high fouling potential. This
blanketing eliminates oxygen which can induce fouling tendencies. Tank seals should be in good
condition before blanketing to prevent loss of the gas. Gas blanketing is one of the most
economical methods to help minimize fouling, but it does not give total protection against fouling.
As stated earlier, many polymerization reactions occur at higher temperatures in the absence of
oxygen.
Many refiners are notching the baffles in heat exchanger to eliminate areas of stagnation where
deposition can buildup. Fouling can begin on or near the baffles and proceed through the
exchanger.
The velocity of the feedstock is another important consideration. If the feedstock is not forced
through the exchanger at a sufficiently high rate, deposits and polymerization can occur and
promote fouling. With sufficient speed, the polymerized products and deposit forming components
of the stream do not have adequate residence time to be left on the exchanger tubes.
Installing feed filters can help to minimize fouling problems that can originate from feedstock in
tankage or from imported feed. Typically, they are most effective at controlling fouling during
periodic upsets. Filter systems often require regular maintenance and only capture particles
greater than the filter pore size. This can result in smaller particles continuing to agglomerate and
potentially deposit on equipment further downstream, especially in the reactor bed.
The development of a good blending protocol could also help to mitigate fouling problems. The
ability to segregate feeds or blend compatible streams can minimize their fouling potential. Feeds
that go straight to the HDS unit from the producing unit and bypass storage normally have a lower
fouling potential, whereas imported feeds or feeds from tankage can have a higher fouling
potential due to possible oxygen exposure. The only drawback to refiners is the reduction in
hydrotreating flexibility for poorer quality feed streams.
Fouling Control Additive Solutions
Chemical solutions are also used to help refiners control fouling. Chemical antifoulants include
dispersants, antioxidants, oxygen scavengers, mercaptan scavengers and metal deactivators.
One of the key components is the dispersant which disrupts polymerization and agglomeration of
the foulant.
Typically, dispersants are used to control fouling in a hydrotreater feed system. A properly
selected dispersant will act on organic polymers to limit gum formation. Dispersants can
minimize the deposition of iron sulfide that forms in situ by keeping particles in a sub micron (< 1
micron) range. A dispersant can act on gums formed by a free radical or condensation
polymerization reaction keeping them finely dispersed and suspended in the process stream
allowing improved operating conditions for a longer period of time. Therefore, a properly selected
dispersant can minimize or eliminate pressure drop concerns in a preheat system and at the
reactor bed.
Dispersants reduce deposition by disrupting agglomeration. They can keep the particles small
enough to remain suspended in the process stream - sub micron size. A dispersant adds a

solubilizing group to improve suspension stability of a potential foulant and limits particle size
growth. Polymers agglomerate to form large particles. If left untreated, these polymers will
agglomerate and precipitate. One action a dispersant adds is steric stabilization of foulant
particles. Basically, this means that a dispersant increases the steric size of potential foulants to
keep polar groups apart, thereby limiting growth. As these very tiny particles enter a reactor, they
will act as the many other organic compounds present in the feed. They can be desulfurized,
denitrified, or hydrogenated. These sterically stabilized particles may decompose somewhat to
smaller molecules, but they will not grow to larger ones within a reactor bed.
Antioxidants and antipolymerants are widely used especially in those cases where a free radical
polymerization reaction is the source for a foulant. If intermediate storage is provided, an
antioxidant should be introduced in the rundown line to tankage. If the formed polymers are
highly crossed linked or highly polar, an antioxidant or an antipolymerant will be needed to block
the polymer formation. A dispersant cannot act on this form of foulant.
Antioxidants act by disrupting the chain reactions of polymerization by limiting initiation steps and
inhibiting propagation or chain extending reactions. Antioxidants will increase the rate of
termination. Hence, they terminate formation of free radical chains. Antioxidants can also inhibit
peroxide induced carbonyl formation that in turn impacts polymer formation via condensation
polymerization.
Fouling Rate Monitoring
Because fouling is seen as a drop in heat transfer efficiency or as a pressure drop limitation,
monitoring is needed to show the influence of fouling mitigation actions on the specific limitation.
For pressure drop limitations, tracking the specific pressure drop over time will be effective. The
increase in pressure drop will appear as an exponential curve rising sharply near the end of a run.
If the feed rate is changed significantly, variations in pressure drop can occur because pressure
drop is proportional to the square of the mass flow rate.
If the limitation is related to heat transfer efficiency, then a temperature survey across the preheat
exchangers is typically performed. In some cases, the reactor effluent temperature to the
separator is sufficient to show the effects of fouling or its control. In other cases, calculating and
trending duty and U value over time for the preheat exchangers can be used to show effects of
treatment. In other cases, a rigorous model that calculates actual fouling resistance for the
affected exchangers may be needed. Again, the variables selected to show performance should
be trended over time. In addition to measuring pressure drop and heat transfer efficiency,
measuring temperature and throughput can also be useful parameters to monitor fouling control
on the unit. Feed characterization can also be performed on the feedstocks to the unit to monitor
the fouling potential of the streams over time. All fouling control programs should incorporate a
comprehensive monitoring strategy.
Case History
The following case history is an example of Baker Petrolites root cause analysis approach to
identify the source of the fouling problem and mitigate the fouling via chemical and operational
solutions.
Problem
A Gulf Coast refinery was having problems with fouling in the preheat section of the distillate
hydrotreater. The fouling was suspected to be occurring on the feed side of the feed/effluent
exchangers. The unit was experiencing severe fouling and the reduction of unit feed rates with
run lengths on the preheat exchangers of about three months.
The refiner requested a meeting and input from Baker Petrolite to investigate the problem. After
meeting with the engineering staff, a plan was put in place to identify the problem, test the feed
streams and identify a program to mitigate the problem.

The problem was believed to involve only one stream being fed to the unit. The feeds to the DHT
were coming from several units in the refinery as hot rundown, and from storage. The Baker
Petrolite technology group determined that the streams should be evaluated individually, and as a
blend. In addition to the suspected streams, the refinery knew there were problems with the
nitrogen blanketing system on the stored feed in tankage. The feed streams were sampled and
evaluated in our laboratories for the existence of fouling precursors, existent gums and potential
gums.
Solution
Based on the information and test results from the feed characterization, the Light Cat Gas Oil
(LCGO) was identified as the primary fouling stream. The LCGO was stored in a blanketed tank
prior to being fed to the DHT. In addition to identifying the specific stream, a likely mechanism
was identified. With this information, the Baker Petrolite technology group was able to choose
suitable products for further laboratory testing.
The fouling mechanism identified in the laboratory tests was sulfur or H2S induced polymerization.
Based on this laboratory testing, Baker Petrolite identified a proprietary antifoulant as the product
of choice for treating the problem stream. Other recommendations offered by Baker Petrolite
included an improvement of the blanketing system on the feed tank and a capital improvement
project to feed the LCGO directly to the DHT. Each of these solutions would have provided
improvement to the system as well.
The recommendation, based on the laboratory testing, was to treat the LCGO stream with best
performing antifoulant at a dosage of 20-40 ppm (by volume), prior to storage. The LCGO was
about 25% of the total feed to the DHT. Treating only the problem stream minimized program
costs, resulting in a significant ROI for the refiner. The program was initiated after the DHT was
shut down and the preheat exchangers cleaned.
Results and Benefits
Under ideal conditions, the DHT would be shut down, and the preheat exchangers cleaned once
a year. The refinery is currently in its 19th month of the run since initiating treatment, with little or
no fouling noted in the system. This case history is presented for illustration purpose only as
results may vary between applications.
The estimated return on the fouling control chemical program is over 200 percent. This value
considers only improvements in throughput and fuel efficiency (less furnace firing) and assumes
no mechanical outages.
Other savings not considered in this economic evaluation include deferred capital expenses to
modify the system to reroute the LCGO feed stream directly to the DHT unit, and for
improvements to the gas blanketing system on the LCGO feed storage tank.
Summary
Fouling in distillate hydrodesulfurization units is caused by inorganic materials from upstream
operations and from polymeric compounds which are formed from the feeds being processed. As
a result of the increase in HDS operating severity to achieve high sulfur removal efficiency, an
increase in the incidence of fouling has been observed in these units around the world. However,
various operational changes or fouling control additive programs can be used to control fouling
rates. Proper identification of the nature of these materials is a key to developing effective
mitigation solutions.

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