WATER WASH INJECTION SUMMARY:

Proper wash water injection is important in maintaining reliable operation of the overhead
condenser circuits and vessels in the Main Column and Gas Concentration Sections of the FCC
Complex. Diligent wash water monitoring, distribution, and control will reduce corrosion and
fouling rates, hydrogen blistering, and weld cracking problems. Proper wash water control will
also minimize the risk of gasoline corrosion problems caused by the formation of elemental
sulfur and will reduce the accumulation of heat stable salts in the amine treating system.

A summary of UOP’s recommendations concerning the operation and monitoring of the wash
water system can be found below. Please refer to the attached document for detailed technical
information and discussion regarding wash water systems.

Recommendations:

1. The pH of the wash water from the main column receiver should always be maintained
between 8.0 and 9.0.

2. The pH of the High Pressure Receiver water boot should be maintained above 7.5 and/or as
high as feasible while maintaining the main column receiver / reflux drum water boots below
a pH of 9.0.

3. The pH of the wash water from the main column receiver and the High Pressure Receiver
(HPR) water boots should be field checked at the FCC Unit on a regular basis. The
laboratory pH values are almost always higher than the field samples due to the samples
releasing hydrogen sulfide before they are tested in the laboratory.

4. The fresh wash water should contain minimum contaminants (salts or dissolved oxygen).
Recommended wash water sources are oxygen free water and boiler feed water before
alkalinity adjustment.

5. The amount of “free water”, percentage of the wash water injected, at the inlet of the
condensers should always be maintained above 10% to prevent salt formation in the
condensers.

6. Depending on feedstock contaminants and processing conditions, it may be difficult or

impossible to meet both the minimum free water recommendation and the pH
recommendations with the conventional wash water design. In units where this has shown
to be a problem (heavily hydrotreated feedstocks, high C3+ recovery, or high Gas Con
pressure), the addition of two relatively minor wash water lines can “de-couple” the water
injection between the Gas Con and Main Column. This provides the degree of freedom
required to maintain proper operation.

7. If the wash water system is modified to provide “de-coupled” operation, the amount of water
to the HPR should only be reduced by enough to provide for proper pH control of the
aqueous phase. Further reduction could allow for undue increase of cyanides to the fuel
gas amine absorber.

THIS DOCUMENT CONTAINS UOP TECHNICAL INFORMATION. DO NOT COPY OR DISSEMINATE

WATER WASH TECHNICAL DISCUSSION
Water Wash Overview:

The overhead stream from the main column contains various contaminants which can cause corrosion,
fouling or plugging of associated downstream equipment, or off-spec product quality. These
contaminants include ammonia, sulfides, cyanides, chlorides and phenols. Most of these contaminants
are ionic or polar in species. As such, they are readily soluble in water and can be removed from the
system through a properly controlled water wash program.

To maintain an effective water wash program while maximizing the long term reliability of the
equipment, it is important to maintain the following:

• Free water at the point of injection.

• Proper pH control of the fresh wash water and outlet sour water.
• Oxygen-free wash water.
• Minimum contaminants in the fresh wash water.

The importance of each of these criteria will be discussed in detail within this paper.

Corrosion Issues:

There is always water present in the Main Column and Gas Concentration Units. The majority of the
water is condensate from the steam flows to the reactor riser and stripper. In the absence of wash water
injection, the condensate from the reactor would become highly corrosive due to the resultant
concentration of sulfides, ammonia, cyanides and other species present in this system.

In some units, sulfide levels greater than 20,000 ppm have been reported in the overhead receiver water.
At these levels, hydrogen blistering and general corrosive attack can become quiet severe, especially if
the concentration of sulfur in the feed is greater than 1 wt.%, or if the nitrogen concentration is greater
than 1000 ppm. With the injection of wash water, the concentration of corrosive species is diluted,
lowering the probability of severe corrosion.

In addition to sulfides, cyanides also play an important role in corrosion and hydrogen blistering. Most
refiners have found that cyanides can be effectively controlled within the Gas Concentration Unit through
the use of adequate water wash to the main column overhead receiver and to the wet gas compressor
inter-stage suction drum. In refineries practicing proper water wash procedures with UOP designed
systems hydrogen blistering has not typically been a problem. An effective water wash dilutes, dissolves,
and flushes the corrosive species such as hydrogen sulfide, ammonia, chlorides and cyanides from the
FCC light hydrocarbon streams.

Product Quality Issues:

The water in the Gas Concentration Unit may become acidic from H2S and CN -. If there is any oxygen
present, elemental sulfur can be formed from the oxidation of sulfides. Elemental sulfur will cause
problems in meeting gasoline product specifications (copper strip corrosion). With the injection of wash
water, the pH can be controlled between 8.0 and 9.0 which will greatly reduce the amount of sulfides that
are oxidized.

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Fouling Issues:

Until about 1980, UOP designed for 100% of the wash water coming from the high pressure receiver to
be injected just upstream of the main column trim coolers. While the provision was included to allow for
occasional water washing of the fin fan exchangers if required, this was not the normal mode of
operation. As refiners moved towards processing dirtier feeds, UOP moved the wash water injection
point to the inlet of the fin fan condensers and maintained the wash water rate at ~1lb/hr per BPSD raw
oil feed.

As the wash water is injected into the overhead condensers, the majority of the water flashes. The amount
of water that flashes is dependent upon the partial pressure of water at the temperature, pressure and
hydrocarbon rate at the point of injection. To maintain trouble free operation, it is critical that there be
free water at the point of injection upstream of the condensers. The “free water” is the amount of water
which remains in the liquid phase immediately after the point of injection.

If free water does not exist at the inlet of the condensers, there will be a “high tide” zone in the exchanger
where the stream temperature reaches the point of initial condensation. Without liquid water present
before this point, a salt ring will form at the interface. As the salt ring continues to form, there would be a
continual loss in heat transfer capability as well as increased back pressure on the reactor system.

The current UOP design criterion for a new unit is to provide for a minimum of 10% free water at the
inlets of the condensers. Though there are occasional exceptions, historically this quantity requirement
has been satisfied at values between 6 - 7 vol.% wash water on fresh feed.

Basis for Free Water Criteria:

On occasion, clients have noted that UOP’s design criteria for 10% free water is significantly lower than
the recommendation of other licensors and industry leaders. In this observation, it is important to note
that water flash in a mixed hydrocarbon stream is very dynamic and difficult to calculate and predict.
One licensor A typically recommends that 30% free water be used to ensure proper washing. One Refiner
typically recommends 25%. Why then does UOP design for only 10% free water? The answer is in the
historical reference data compared to the calculation methods employed.

Wash water systems have been employed since the advent of FCC Units in the early 1940’s. As such,
there exists a lot of operational and maintenance histories to evaluate which wash water rates provide for
trouble free operation. In calculating the free water at the inlet of the main column overhead condensers,
UOP uses its own proprietary Engineering Program to perform the flash calculations. Others rely on
Hysis, Hysim or their own internal models. Regardless of which model is most accurate, there are distinct
differences between calculations methods used. When the free water recommendations of 10% (UOP),
25%(Refiner B) and 30% (Licensor A) are compared on a mass basis, we find that all three
recommendations are almost identical in mass per unit time. The percent recommendations simply use
different calculation methods, referenced to historical data to end up with essentially the same
recommendation. While the percentages are calculated to be different, the water wash mass flow rates at
a given set of processing conditions are essentially the same.

As there are operating penalties involved with too little wash water, there are also penalties involved with
excessive wash water. Regardless of the criteria chosen as a guideline for wash water injection, the
optimum value for each unit is dependent upon the type and concentration of contaminants in the feed.
To minimize operating cost and to maximize unit reliability, every refiner should maintain a continual
monitoring program of the wash water and sour water quality in order to assure the mechanical reliability
of the unit.

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Wash Water Sources:

The purpose of the wash water is to remove potentially harmful contaminants, not introduce them. For
this reason it is important that the make-up wash water be clean. As such, UOP recommends the use of
steam condensate for wash water service. The cleanliness of the make-up wash water is important to
prevent problems resulting from salts or dissolved oxygen being injected into the system with the water.
Other recommended wash water sources include oxygen free water and boiler feed water before alkalinity
adjustment. If the wash water contains oxygen, gum formation will increase and fouling of the Wet Gas
Compressor may occur. The presence of oxygen in the Gas Con can also result in the formation of
elemental sulfur which leads to corrosive gasoline. Furthermore, if the wash water contains magnesium
or calcium salts, the salts will precipitate out and increase the fouling problems in the unit.

Note: While all gasoline will be somewhat corrosive, the term “corrosive gasoline” in this paper, refers
to gasoline which fails the ASTM D-130 “Detection of Copper Corrosion from Petroleum Products by the
Copper Strip Tarnish Test”; a result of >1B (i.e. 2A..2B..& greater) on the measurement scale.

In some cases refiners have also used treated sour water as a portion of the total wash water in order to
reduce operating costs. This practice has been found to be acceptable as long as the treated water quality
is good. However, as a guideline, UOP recommends that at least 50% of the wash water be fresh clean
water to prevent the buildup of phenols in the system.

Water Injection Systems:

The actual mechanics of injecting wash water into inlet of the condensers is not complicated. A
simplified Process Flow Diagram of the UOP Wash Water System is shown in Attachment “C”. After the
proper water flow rate is established on the flow meters, the water injection to each of the individual
condensers in the system is balanced through the use of restriction orifices (RO’s) as shown in the
following diagram. The RO’s are equipped with break flanges and isolation valves to allow for removal
and cleaning of the RO should it become fouled. The bypass around the RO is to allow for periodic high
volume flushing of the exchanger if a high degree of localized fouling is observed in a particular
exchanger. It is important to note that use of the bypass line should not be considered for long term
operation. The high volume flushing of a single exchanger will result in mal-distribution of water to the
other exchangers and over-washing of that exchanger.
Overhead
Vapor Line

RO

Wash Water min.

Injection

Fin Fan Condenser

HC

M M
To Wet Gas
Compressor

Trim
Condensers

Receiver

Distributor (Slot Facing End Of Drum)

Closed End

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Although UOP does specify the use of injection quills for injection of chemicals into liquid streams to
ensure good additive distribution, in general UOP has not found injection quills to be necessary for FCC
water wash service. Typically, the vapor steam into which the wash water is injected is in the turbulent
flow regime. The water is adequately distributed into the vapor flow through the mixing created by the
pipe inlet to the exchanger. If desired by a client, UOP does not have any objections to the use of quills
for water injection into vapor phase streams.

The sketch below shows a simple closed pipe water wash distributor with a side oriented hole drilled to
provide co-current water spray discharge into the flowing vapor phase. This is a very simple device
which is common within the refining industry. The sketch below shows that the distributor discharge is
on the centerline of the vapor inlet pipe to the exchanger and is flanged for maintenance and inspection
during shutdowns.

On occasion, refiners have asked if the distributors can be made retractable to provide for easier
maintenance should the distributors become plugged. UOP does not consider distributor insertion
through a packing gland and gate valve for "retractability on the run" acceptable for hydrocarbon service.

Dhole

When accommodating a client request for injection distributors, UOP still maintains the requirement for
restriction orifices located upstream of the isolation valve as the means of regulating flow to the water
wash points. In this case, the hole in the distributor is larger than the hole in the upstream RO so that any
large debris would accumulate at the RO where it can be isolated and cleaned while in operation.

The ΔP across the distributor hole does not need to be large to generate an effective water wash spray
pattern. However, the sizing of the RO and the quill discharge hole need to be designed to ensure that the
sizing of the holes are consistent with the desired water wash rates.

Counter-Current vs. Co-Current Wash Water Designs:

UOP wash water systems are “counter-current” in design. Steel corrosion and hydrogen blistering are
accelerated in high pressure, high contaminant environments. The UOP counter-current wash water
system is designed to minimize the contaminants in the high pressure section of the unit by injecting the
fresh water into the high pressure section of the unit where the concentration of cyanides is lowest.

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As shown in Attachment “C”, the wash water in the UOP designed system is first injected into the inlet of
the Wet Gas Compressor Inter-stage Cooler. This water is eventually collected in the water boot of the
High Pressure Receiver (HPR).

The partially contaminated wash water from the HPR is injected into the inlet of each main column
overhead condenser. When the water enters the low pressure main column overhead system most of the
cyanide and hydrogen sulfide flash on initial injection. In recognizing this phenomenon, properly locating
the point of injection is critical. The overhead condensers act as very efficient mixing systems, providing
for the majority of the cyanide and hydrogen sulfide to be re-absorbed into the water and removed from
the system. The heavily contaminated water is sent from the main column overhead receiver boot to the
sour water stripping unit for hydrogen sulfide, ammonium bisulfide and cyanide removal.

UOP has been questioned many times regarding the effectiveness of the counter-current wash water
design, even to the point of some insisting that it does not work. With well over a hundred units licensed,
there is no question that the system works well. UOP believes that the confusion over this issue stems
from the poor result of an experiment that did not properly model the UOP design.

The experiment in question was conducted several years ago by Amoco. In the experiment, Amoco tried
injecting fresh water between the first stage of the wet gas compressor and the knockout drum. The water
was then pumped into the line after the second stage of compression. The water from the HPR was then
injected into the main column overhead receiver at a point just below the off-gas line. As the hydrogen
sulfide, ammonium bisulfide and cyanides flashed, they did not have sufficient contact time or space for
the contaminants to be re-absorbed into the wash water before exiting the receiver to the wet gas
compressor. This resulted in a continual recycle of contaminants that eventually fouled and damaged the
equipment. The point of injection on the receiver was chosen at a location different than the UOP design
as UOP had patented the idea of injecting the water upstream of the fin fan condensers.

Joerg Gutzeit, now several years retired from Amoco, authored a NACE technical paper on corrosion in
which the results of this experiment were published. UOP believes that the confusion over the
capabilities of a counter-current wash water system is a result of this technical paper inappropriately
categorizing all counter-current designs as bad and not recognizing the differences between the UOP
design and the experiment. Within UOP designed units, a multitude of “spot tests” have been run over the
years on the wash water from the HPR water boot. Typically, only a trace of cyanide has been present.
This indicates both good contacting and adequate quantity of wash water being injected.

UOP believes that contamination concerns are higher in a co-current wash water system. This position is
supported by the fundamental chemistry involved with hydrogen blistering as outlined later in this paper.
In a co-current system, the fresh water is injected into the overhead line of the main fractionator, washing
the majority of the contaminants out of the light hydrocarbon stream. The water from the main column
receiver is pumped into the line between the first stage of compression and second stage of compression.
The water from the first stage is again pumped to the line after the second stage of compression for the
final wash. This water contains the highest concentration of cyanide in the system. The high cyanide
content will always fail the “spot test” and any water carried over into the gas concentration system will
contain sufficient cyanides to cause hydrogen blistering in the first column, typically the Stripper. In the
counter-current scheme, any water carried over into the gas concentration system contains minimal levels
of cyanide, thus minimizing the potential for hydrogen blistering.

Condensate pH:

The pH of the water from the high pressure receiver, main column overhead receiver / reflux drum,
should always be maintained in a range of 8.0 to 9.0. Operation outside of this recommended range,

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either higher or lower, can cause problems with product specifications (corrosive gasoline) or corrosion of
the unit.

The overhead streams in the main column and the gas concentration unit consist mainly of hydrocarbon
vapors, steam and relatively small amounts of contaminants. As the water vapors condense, the aqueous
phase absorbs some of the contaminants and can become highly corrosive. As has been noted above, if
no additional wash water is added to the system, the pH of the aqueous phase can become acidic and
corrosion and hydrogen blistering can occur. Historically, when a pH neutral (7.0) wash water has been
used, the FCC process condensate typically develops a pH of 8 to 9. This is due to the fact that the
ammonia present in these streams is more soluble in water than hydrogen sulfide or hydrogen cyanide and
has also typically been present in a higher concentration. While this trend has shifted in recent years it
does not change the pH target for the aqueous phase. The shift in relative contaminant concentrations
will be discussed in detail later in this paper.

NOTE: When analyzing the pH of the wash water / sour water, from the high pressure receiver and the
main column receiver / reflux drum it is very important that the pH measurement of the water be made
at site with a portable pH meter. If a sample is allowed to sit for any period of time, hydrogen sulfide
will evolve out of the sample. This can change the measured pH of the wash water by as much as 2 pH
units.

Wash Water Condensate pH (Upper Limit – pH > 9.0):

During normal operation, the refiner will always experience a certain amount of ammonia attack on
Admiralty Brass tubes in the condensers or coolers. If proper wash water injection is not maintained, the
ammonia attack can become quite severe. Stress corrosion of brass tubes may be seen in exchangers
where the pH has been maintained, or allowed to range too high (>9.0). The maximum recommended pH
has therefore been set to limit the corrosion rate of the Admiralty Brass exchanger tubes.

Wash Water Condensate pH (Lower Limit – pH < 8.0):

If the pH of the aqueous phase in the overhead systems is allowed to range too low the corrosion rate of
carbon steel increases rapidly. When the pH is <8.0, H2S can easily oxidize in the presence of oxygen,
oxygen-bearing compounds, and acidic or neutral sulfur. The corrosivity of petroleum products is due
exclusively to the presence of S0, H2S and polysulfides.

One oxygen source that is always present is the fluidization gas in the catalyst circulating from the
regenerator to the reactor. This oxygen however, does not typically cause a problem with elemental
sulfur formation. Most of this oxygen is rapidly consumed in various organic reactions to produce
phenols, aldehydes, alcohols, thiophenols, carbonyl sulfide and others, as H2S is simultaneously formed
in the reactor. Although some refiners have tested and found CO2 in the reactor, this is probably from the
catalyst circulation and not a reaction product, since the concentration of oxygen from the catalyst
circulation is well below the flammability limit for any of the hydrocarbon components present. The net
result is that the oxygen from the circulating catalyst and the H2S formed by the process, are not present
in the reactor at the same time in sufficient quantity to cause a problem with elemental sulfur formation.

The most common source of oxygen in the gas concentration section is from the wash water itself. If
there is any dissolved oxygen in the wash water, this oxygen will be intimately contacted with the H2S
and efficiently converted to elemental sulfur. This is the basis for the previous recommendation that the
water wash sources include oxygen free water and boiler feed water before alkalinity adjustment.

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Though the following three reactions can promote elemental sulfur formation, reaction #1 is the most
common. Reaction #3 helps explain why refiners often see corrosive gasoline for a few days following a
Turnaround when all the vessels have been opened and rust forms on the vessel walls:

1) 2 H2S + O2 → 2 S0 + 2 H2O
2) 2 H2S + H2SO3 → 3 S0 + 2 H2O
3) H2S + Fe2O3 • H2O → S0 + 4 H2O + 2 FeS

In addition to the metal corrosion that can be observed in the unit due to low aqueous phase pH, elemental
sulfur levels of ≥1 wppm will cause corrosive gasoline. Since elemental sulfur formation is more likely
under acidic conditions, product quality requirements can be difficult to meet if the aqueous phase pH is
not properly controlled. Many times when the FCC Unit operations have been adjusted for particularly
high C3 recovery (for example above 95 %), corrosivity of the FCC gasoline has been observed. The
higher partial pressure of H2S in the HPR, absorber, and stripper system, which is a consequence of
increased C3 recovery, often results in low aqueous phase pH, which favors reaction (1) proceeding. For
this reason, when adjusting the FCC Unit for higher C3 recovery, it is important to simultaneously check
the pH of the FCC condensate.

Controlling the Aqueous Phase pH:

When adjusting the pH of the condensate, it is not always readily obvious whether the fresh water make-
up should be increased or decreased. This is due to the balance which exists between the pH of the fresh
water, the concentration of ammonia present and the concentration of acidic components present. If the
FCC Unit feedstock contains a lot of nitrogen and little sulfur, the aqueous phase pH will typically be
high. In this case, the pH can be lowered by increasing the fresh water rate.

If the FCC Unit feedstock nitrogen level is low, consistent with heavily hydrotreated feedstocks, the pH
of the receiver water will tend to be low. In this case, the low pH can often be increased by lowering the
fresh water rate. Care must be taken however, not to lower the rate so far as to eliminate the presence of
free water at the exchanger inlets and allow salt deposits to form. This situation is becoming more
prevalent as refiners increase the degree of hydrotreating of FCC feedstocks.

As feedstocks are more heavily hydrotreated and the nitrogen levels are reduced, given a fixed wash
water injection rate to the main column condensers, less ammonia is rejected to the gas concentration unit.
Another way of viewing this situation is that a higher percentage of ammonia is absorbed in the main
column section. Since the ammonia in the system provides the basic component of the aqueous phase pH,
once it has been mostly absorbed in the main column section, there is little present to help buffer the pH
in the HPR water boot. As a result, the pH in the HPR water boot decreases as the primary contaminants
shift to an increased percentage of acidic H2S and HCN- components. In this situation, when the pH of
the HPR water drops below 8.0, the wash water rate must be decreased to reject more H2S and HCN. The
lower limit for the wash water injection rate is set by the 10% free water requirement at the inlet of the
exchangers. This situation becomes problematic when the wash water requirement to maintain proper pH
of the HPR drops below the free water requirement of the main column system.

When the aforementioned situation occurs, older unit designs do not have a piping configuration that
provides for proper balancing of the HPR water boot pH while adhering to the minimum water injection
rate to the main column condensers.
This situation can be further aggravated if a refiner maintains a higher than design operating pressure in
the absorber section of the Gas Concentration Unit. This is typical of refiners trying to minimize C3=
losses to fuel gas at maximum throughput. This is accomplished by maximizing the lean oil circulation
rates and the operating pressure of the Gas Con. As the C3+ in the fuel gas is driven lower by increased

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lean oil flow and Gas Con pressure, the partial pressure of H2S and CN- is increased in the HPR system.
This drives down the pH of the HPR water boot. This phenomenon tends to become a problem when
refiners try to operate with less than ~5 mol% C3+ in the fuel gas from the back end of the Gas
Concentration Unit. As previously stated, the low water pH which results from the higher H2S partial
pressure promotes the formation of elemental sulfur. In addition, the higher H2S partial pressure at low
pH results in higher concentrations of bisulfide (HS-) which also increases the steel corrosion rate in the
unit.

Wash Water System Design Modification (January, 2002):

Problem Presented by Low Nitrogen Feedstock:

As previously noted, when adjusting the pH of the overhead system aqueous phase, it is not always
readily apparent whether the fresh water make-up should be increased or decreased to achieve the proper
adjustment. The pH response to a change in wash water rate is dependent on the concentration of
ammonia versus the concentration of acidic components present. These contaminants can shift with the
concentration and species of nitrogen and sulfur in the feed as well as the operating conditions in the
absorber section of the Gas Concentration Unit.

Recently, UOP has observed that some refiners who process heavily hydrotreated feedstocks have
experienced problems with proper pH control of the wash water system. In one case the refiner increased
the wash water rate in response to low pH in the HPR water boot and observed a further decrease in HPR
water boot pH. The wash water was then gradually decreased until the pH was above pH 7.5. Although
this was desirable, the water injection rate had to be lowered to a point where there was no free water left
at the inlet of the main column overhead condensers. This resulted in fouling of the condensers. This
process of trial and error was repeated several times with the same result.

Potential Resolutions to pH Imbalances:

Although relatively rare, when a refiner has hit a limit on minimum wash water and low HPR sour water
pH, ammonia injection has been added to the overhead of the main column or directly into the fresh
makeup water. The quantity of ammonia injection that would be required for each refiner is dependent
upon feed contaminants and the starting pH of the fresh wash water. While this solution has proven to be
effective, it increases the operating cost of the unit by requiring the consumption of ammonia which must
then be removed in the sour water stripper. As such, a better engineering solution is desirable.

In response to the refiner’s needs, UOP completed a detailed review of the wash water system that has
been the UOP standard design for many years. This review identified a relatively simple design addition
that greatly increased the operating flexibility of the wash water system and provides the refiner with both
proper pH and free water control.

Until recently, 100% of the wash water required to maintain free water to the inlet of the main column
condensers had to be supplied through the HPR system. This did not provide the degree of freedom
needed to control both free water and pH specifications in as previously detailed. The extra degree of
freedom needed to enable proper operation can however, be provided by the installation of two additional
wash water process lines. These two lines include a spillback line from the discharge of the MC Receiver
sour water pumps to the inlet of the main column condensers, and a fresh water make-up line directly to
the inlet of the main column condensers. Both the previous design configuration and the additional
process lines are shown in Attachment “C”.

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In the new control scheme, the rate of fresh wash water to the interstage condenser is reduced to maintain
9.0 ≥ pH ≥ 8.0 in the HPR water boot. With the relatively low temperature and high pressure of the
interstage receiver, there is little trouble ensuring free water at the inlet of the condensers. As the
injection of fresh water is decreased, the recycle of water from the main column overhead receiver water
boot back to the inlet of the main column condensers would be increased to maintain >10% free water at
the inlet of the condensers. This is accomplished through the new process line marked “(1)” in
Attachment “C”. To prevent the accumulation of contaminants in this new water recycle, the piping
system is sized for a maximum flow of 50% of the total water circulation through the condensers.

This is not to say that the wash water split between the HPR and the main column receiver should be
50/50. Rather, the wash water to the HPR should only be decreased enough to maintain a water pH >7.5.
As the wash water injection to the HPR is decreased, directionally, the amount of CN- in the fuel gas will
increase. This increases the tendency to form heat stable salts in the amine absorber. If this is observed,
the recycle around the main column receiver can be increased beyond ~10% free water to improve the
water / hydrocarbon contacting.

When using the sour water recycle, the UOP recommended limits for sour water contaminants are shown
in the following table. A listing of appropriate sample methods is shown in Attachment “A”. It is most
important that the ammonium bisulfide concentration (NH)4HS never be allowed to exceed 0.8 wt.% in
the sour water. If the ammonium bisulfide increases above 0.8 wt.%, the sour water recycle rate should
be reduced, and supplemental fresh wash water added through the line marked “(2)” in Attachment “C” to
maintain ≥10% free water at the inlet of the condensers. Higher bisulfide concentrations increase the
corrosion rate in the unit as detailed in the following section of this paper.

Sour Water Contaminants

Wash Water Contaminant Recommended Limits
Ammonium Bisulfide < 8.0 wt.%
Cyanides < 30 wppm
Iron < 1 wppm
Ammonia Sour Water 8.0 ≤ pH ≤ 9.0
Hydrocarbons <2000 wppm;
Dependent on Treating Unit
Limitations
Phenols 50 – 500 wppm;
Dependent on Treating Unit
Limitations

This newly modified flow scheme provides the following benefits:

• Increased control of wash water pH in HPR and MC Overhead Receiver.

• Minimized wash water consumption.
• Minimized sour water production.

Steel Corrosion And Hydrogen Blistering:

Steel corrosion, hydrogen blistering and weld cracking problems can result from an environment
containing water, hydrogen sulfide, ammonia and / or cyanides. Within this hostile environment, the
overall corrosion reaction for steel is:

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 1) Fe° + 2 HS - → FeS + S -2 + 2H°

The bisulfide ion (HS-) is generated by the dissociation of H2S. The quantity formed depends on the pH,
temperature and hydrogen sulfide (H2S) partial pressure:

2) H2S → H + + HS –

Or

3) 2H2S + 2NH3 ↔ 2(NH4)HS ↔ 2NH4 + 2HS -

The iron sulfide (FeS) scale provides some protection against corrosion if the system pH is ≥ 8.0.
However, as the pH is lowered, the dissolved hydrogen cyanide (HCN) accelerates corrosion by
destroying the protective FeS film, converting it into soluble ferrocyanide complexes:

4) FeS + 6CN - → Fe(CN)6 -2 + S –2

This reaction has been alternately proposed as:

5) FeS + 6NH4+ + 6CN - → (NH4)4Fe(CN)6 + (NH4)2S

The ferrocyanide (Fe(CN)6-4) is easily recognized by its blue color (Prussian blue) when water samples
are allowed to dry. The presence of cyanides greatly increases the susceptibility of hydrogen blistering in
steel. During maintenance, the refiner should look for a bluish color when the plant is first opened. This
is a good indication of areas where corrosion and/or hydrogen blistering may be found. Although cyanide
is the major contributor, hydrogen sulfide (H2S) also contributes to blistering and corrosion.

Hydrogen blistering occurs in steel where surface corrosion is active. Some portion of the hydrogen
atoms formed in the corrosion process (Equation #1) gradually penetrates the steel through surface
imperfections and diffuses into the steel as atomic hydrogen. The atomic hydrogen then has a tendency to
accumulate at slag or inclusions within dirty steel. This diffusing hydrogen then reacts to form molecular
hydrogen:

6) 2H° → H2

The hydrogen molecules are larger in size and become trapped in the steel cavities causing the local
pressure to increase. The result is hydrogen blistering. These blisters can rupture to the thin side of the
defect. High quality killed carbon steel usually has less inclusions today than in earlier times. As such,
hydrogen blistering is typically less of a problem for newer units.

Polysulfide Injection:

Some Refiners who process feeds with high nitrogen content and have high cyanide concentrations in the
Unit use ammonium polysulfide to reduce the overall corrosion rate. The use of this material is typically
limited to cases where there are restrictions to the amount of wash water that can be used or processed in
the refinery. Again, if the refiner follows the UOP recommended wash water practices, use of polysulfide
injection should not be necessary.

Ammonium polysulfide is an additive that converts cyanides to thiocyanates by the following reaction:

THIS DOCUMENT CONTAINS UOP TECHNICAL INFORMATION. DO NOT COPY OR DISSEMINATE, Page 10 of 21
 7) (NH4)2Sx + HCN → NH4SCN + Sx-1

The refiner should monitor the Gas Concentration Unit carefully when injecting polysulfide, as these
compounds can sometimes cause more problems than benefits. The following are some disadvantages of
ammonium polysulfide:

1. The pH of the system should always be higher than 8.0. At lower pH values the polysulfide
decomposes into ammonia (NH3), hydrogen sulfide (H2S) and elemental sulfur (S°). The H2S will
increase the corrosion rate and the elemental sulfur (S°) will cause corrosive gasoline and equipment
plugging problems.

2. Polysulfide will commence salting out at temperatures below –17.5°C (0°F) which will render the
material ineffective and can result in plugging of pump suction and discharge lines. This requirement
applies to the material from the time it is manufactured through the time it is injected into the unit. It
must be kept above 0°F throughout the entire life cycle of the material. Note: Older literature may
state that the material begins a salt precipitation at 40°F (4.5°C). Advancements in the production
process in ~1996 have provided for a lower allowable handling temperature of the material before a
salt precipitation forms.

3. Polysulfide will decompose at temperatures close to 121°C, producing H2S, NH3 and S°. The H2S
will increase the corrosion rate and the S° will result in corrosive gasoline and equipment plugging
problems.

4. Improper storage can result in the NH3 flashing out of solution, precipitating the sulfur. This will
result in corrosive gasoline and equipment plugging problems. It is critical to follow the vendors
storage recommendations.

5. An excess of 10 to 15 ppm polysulfides over the stoichiometric amount of cyanide is desired.

However, if the concentration increases to over 30 ppm excess polysulfide, there will be enough
polysulfide in the sour water stripper bottoms to cause problems in the effluent treating. Upon
neutralization in the treating unit, the excess (NH4)2S3 decomposes into NH3, H2S and S° which can
result in bacterial kill and equipment plugging in biotreating units.

6. Wash water requirements are generally higher to assure that the polysulfide stays in solution; (higher
than refinery norms, but still less than UOP recommended). If the polysulfide does not stay in
solution, equipment plugging problems will increase. With the increase in wash water requirement,
processing the additional sour water can be costly.

7. The production of ammonium polysulfide has historically been unique to the United States fertilizer
industry as a spray applied fertilizer product. It is not readily accessible in many areas of the world.
Shipping costs can easily become prohibitive. The only supplier of this material currently known to
UOP is:

MPR Services Inc.

Subsidiary of Tessenderlo Kersley
1201 FM 646
P.O. Box 567
Dickinson, Texas 77539-0567

Normally, UOP does not recommend a polysulfide injection program. Rather, we endorse the
implementation of proper water wash techniques for corrosion control. However, if the refiner decides to

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implement ammonia polysulfide injection with the wash water to the main column, compressor interstage
or HPR, it is technically acceptable, provided the preceding precautions are followed.

Phenols:

Phenol, catechol, resorcinol, hydroquinone and cresols all fall within the broad category of aromatic
alcohols. Often times, the lab methods typically used for determination of phenol in sour water streams
are not specific for phenol, but rather detect all the aromatic alcohols. While a component breakdown of
aromatic alcohols is not common, or generally recommended, this is one reason that “phenols” are shown
to exist in multiple fractions from the crude unit. Pure phenol boils at 182°C (360°F) which is on the
heavy end of the naphtha range. Depending on the overlap of the split, phenol can distill to NHT feed,
kerosene or white oil.

The FCC unit produces a quantity of phenols in the cracking environment of the reactor riser. A lot of the
phenol produced is subsequently washed out of the hydrocarbon phase via the water wash system and
leaves the FCC unit with the sour water effluent from the main column overhead receiver. The levels of
phenol present in the FCC sour water generally range from 50 - 450 wppm.

Phenols in the FCC unit to not cause problems in the unit itself, however some refiners have expressed
concern about treating phenols in the sour water since high concentrations can kill many of the microbes
used for treatment. While phenol levels in the FCC sour water generally range up to only a modest ~450
wppm, higher concentrations have been seen. However, with the proper selection of treating organisms,
this can be managed as many biologic treating systems have proven to be successful at treating water with
phenol concentrations up to ~10,000 wppm. It should be noted however, that depending on the efficiency
of operation and desired level of reduction this might on occasion require the use of commercially
available biological populations specific for phenol oxidation.

Reducing Phenol Content of Sour Water:

Some refiners dispose of phenolic wash water by injecting it into the crude unit desalter. Some refiners
reduce phenol discharge by using stripped sour water as wash water in the crude unit. In the first case,
the phenolic material dissolves into the crude oil while the remaining water is decanted away. While this
has shown to be effective at reducing the phenol content to almost zero, if the pH of the wash water is too
high (pH > 9.0) the refiner can experience problems with rag layer stabilization in the desalter. This
however, is consistent with pH recommendations within the FCC Unit and should not be a problem to
accommodate. In the second case, the various hydrocarbon streams in the crude unit absorb most of the
phenols.

Most of the phenol extracted from the water ends up in the fraction that feeds the Naphtha Hydrotreater.
These phenols can be hydrotreated away so long as the catalyst is active and the unit is not being pushed
in capacity. If the phenol is not converted in the NHT, it will readily convert to water in the reforming
reactors. Excessive water (>20 wppm) in the reforming reactors will strip chloride, increase coking and
promote hydrocracking reactions. This can be a significant problem in semi-regen reforming reactors.
While the same is true for Continuous Catalyst Regeneration (CCR) reforming units, with the removal of
phenol from the feed, the unit can recover as the catalyst is re-chlorided in the CCR. As such, when
processing phenolic water in the crude unit desalters, it is important to ensure active catalyst in the NHT.

If the phenol enters the kerosene or white oil fraction, it can produce color problems if the kerosene is not
caustic treated. Caustic treating of the straight-run kerosene removes phenols and other acidic
compounds and is typically practiced in refineries equipped with caustic incinerators.

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Any extraneous oxygen present in the catalytic cracking zone can react to form a variety of oxygen
compounds including phenol. There are two principle production routes for phenols in the FCC unit.
The first is from naturally occurring oxygen containing constituents of the feedstock in which oxygen is
covalently bonded to aromatic structures. In the progression of cracking reactions in the reactor riser,
many of the oxygen bearing compounds form phenols.

The second source of phenol production in the FCC unit is from extraneous oxygen sources. This
includes any dissolved atmospheric oxygen present in the feed (feed stored under air), air purges used on
the FCC reactor and regenerator combustion gases entrained with the regenerated catalyst to the reactor
riser.

By far, the largest contributor to the production of phenols in the FCC Unit is the content of naturally
occurring oxygen in the feedstock. This has been identified by comparing phenol production in units that
process virgin VGO versus hydrotreated VGO. Units that process hydrotreated feedstocks show a lower
phenol production by a factor of 2 to 3 times that of virgin feedstocks.

To date, there are no practical or realistic methods that have been identified for reducing the phenol
production in the FCC unit. As previously discussed, feed hydrotreating can significantly reduce phenol
production but is an expensive option which has to be justified for reasons other than phenol control.
Minimizing extraneous oxygen sources can be helpful, but this source of phenol production is considered
to be a relatively small percentage of the total phenol production.

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 ATTACHMENTS
• Attachment “A”: Recommended Wash Water
Sample Schedule

• Attachment “B”: Typical Wash Water Sample

Results

• Attachment “C”: Current and Proposed Wash

Water Flow Schemes

THIS DOCUMENT CONTAINS UOP TECHNICAL INFORMATION. DO NOT COPY OR DISSEMINATE, Page 14 of 21
 Attachment “A”:

Recommended Wash Water Sample Schedule

STREAM AND TEST TEST NUMBER FREQUENCY

Normal
Main Column Receiver Water
Iron, Copper UOP-314 1/Month
Phenols UOP-262 1/Month
Cyanides UOP-682 2/Month
Sulfides UOP-683 2/Month
Ammonia UOP-740 1/Month
Total Oils D-3921 1/Month
pH D-1293 1/Day
Total Dissolved Solids D-1126 1/Week
Total Alkalinity D-1067 1/Week

THIS DOCUMENT CONTAINS UOP TECHNICAL INFORMATION. DO NOT COPY OR DISSEMINATE, Page 15 of 21
 Attachment “B”:
Typical Wash Water Sample Results

FCC Unit - Main Column Sour Water Inspections

Refiner Refinery A Refinery A Refinery B Refinery C Refinery D Refinery E

Location Texas Texas Midwest Texas East Coast Midwest

Feedstock HT-VGO + HT-VGO + VGO VGO HT-VGO VGO + Coker

Source DMOForeign DMOForeign Canadian + Texas - GO -
°API Gravity 26.4 25.3 L l 26.3 25.7 28.4 26.3
UOP K 11.9 11.8 11.9 11.9 12.1 11.9
Mol Wt 373 439 332 350 - 360
Total Sulfur, wt% 0.12 0.18 0.8 1.71 0.23 1
Total Nitrogen, wt% 0.043 0.113 0.073 0.08 0.076 0.093

Sour Water
pH 9.1 9.25 8.7 8.8 9.25 -
Sulfides, as wppm S 1400 1800 2700 2975 994 3630
Mercaptans, as wppm S 96 0 0 128 800 -
Ammonia, as wt% 0.31 0.45 0.19 0.141 0.09 0.29
NH3
Total Alkalinity, as wt% 1.06 1.04 0.43 0.42 0.19 -
N OH Alkalinity, as wt%
Strong - 0.46 - - - -
N OHSolids, wt%
Total 0.011 0.019 0.09 0.0084 0.0095 -
Iron, wppm < 0.05 < 0.13 30 6 0.18 -
Copper, wppm < 0.01 < 0.01 < 0.5 < 0.02 < 0.01 -
Chloride, wppm - 6 5 26 56.2 -
Phenols, wppm 65 65 160 424 65 304
Cyanide, wppm 25 23 57 50 2 40

FCC Unit - Main Column Sour Water Inspections

Refiner Refinery E Refinery F Refinery F Refinery G Refinery G Refinery H

Location Midwest Midwest Midwest Japan Japan Japan

Feedstock VGO + Coker Reduced Crude Reduced Crude HT-VGO HT-VGO HT-VGO
Source GO - Various Illinois - - -
°API Gravity 26.3 - - 34.6 - -
UOP K 11.9 - - - - -
Mol Wt 360 - - - - -
Total Sulfur, wt% 1 - - - - -
Total Nitrogen, wt% 0.093 - - - - -

Sour Water
pH 8.6 9.1 8.95 7.8 8.8 9.8
Sulfides, as wppm S 1700 3300 1930 2000 500 2600
Mercaptans, as wppm S 210 2200 190 - - -
Ammonia, as wt% 0.16 0.288 0.199 0.12 0.11 0.175
NH3
Total Alkalinity, as wt% 0.37 0.71 0.41 - - -
N OH Alkalinity, as wt%
Strong - 0.26 - - - -
N OHSolids, wt%
Total 0.02 0.05 0.04 - - -
Iron, wppm 1.2 < 0.01 0.16 0.3 1 -
Copper, wppm < 0.0015 < 0.01 0.11 0.2 0.2 -
Chloride, wppm 11 31 37 - - -
Phenols, wppm 340 376 162 - - 64
Cyanide, wppm 41 88 24 - - 74

THIS DOCUMENT CONTAINS UOP TECHNICAL INFORMATION. DO NOT COPY OR DISSEMINATE, Page 16 of 21
Attachment “C”:

Current and Proposed Wash Water Flow Schemes

THIS DOCUMENT CONTAINS UOP TECHNICAL INFORMATION. DO NOT COPY OR DISSEMINATE, Page 17 of 21
 Typical Wash Water System: Single Drum Receiver Systems
(Process Line Additions Shown as c and d)

Main Column Condenser

Main Column Trim Condenser

Comp
Suction
LIC
Drum

Main Column
Receiver

LIC

Normally No Flow To Gas

Wet Gas Compressor
Concentration
Main FRC
Section
Column

1 To Waste Water
Stripping Unit

Interstage Cooler

High Pressure Condenser

Interstage Trim Cooler

High Pressure Trim Cooler

Interstage
Suction LIC
Drum

FRC

High Pressure
Water
Receiver
Break
Tank
LIC

FRC

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 Typical Wash Water System: Two Drum Receiver Systems
(Process Line Additions Shown as c and d)

Main Column Condenser Main Column Trim Condenser

Comp
Suction
LIC
Drum
Main Column Main Column
Reflux Drum Receiver

LIC LIC

Normally No Flow To Gas

Wet Gas Compressor
Concentration
FRC
Main Section
Column

1 To Waste Water
Stripping Unit

Interstage Cooler

High Pressure Condenser

Interstage Trim Cooler

High Pressure Trim Cooler

Interstage
Suction LIC
Drum

FRC

Water High Pressure

Break Receiver
Tank

LIC

FRC

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