Preventing salt fouling in FCC main

fractionators
Results of using salt dispersant additives on a badly fouled FCC unit show the
method allows refiners to avoid more costly methods of naphtha fractionation
David O Martin Nalco/Exxon Energy Chemicals
Richard O Allen Texaco Ltd

ow sulphur gasoline specifications for both

European and US markets will require new
technologies to allow refiners to meet these
requirements. Process licensors are introducing
new processes for sulphur removal from gasoline,
focusing in particular on the FCC naphtha. To
take advantage of these processes and minimise
octane loss, some form of FCC naphtha fractionation will usually be required, followed by
treatment of the heavy naphtha fraction.
Depending on the fractionation option chosen,
modifications and operating changes to the FCC
main fractionator may be required. These changes
may include direct undercutting of the FCC naphtha, separating the heavy, high-sulphur naphtha
via a heavy naphtha draw.
At the same time, FCC feeds are becoming
increasingly heavy. Processing of atmospheric
residue is becoming more common. Residues
typically contain at least traces of chloride salts.
These trends can lead to conditions in which
ammonium chloride salts can deposit in FCC
main fractionators and overheads, due to the
combination of low temperature and relatively
high concentrations of ammonia and hydrogen
chloride. The build-up of salt deposits normally
occurs in the mid-to-upper sections of the main
fractionator column and top pumparound circuits.
If not removed, these salts will accumulate to the
point where they can cause a number of problems
in maintaining optimal tower operation, and ultimately affect the operation of the entire FCC unit.
Salt deposition is becoming an increasing
concern.
Traditional methods of preventing salt deposition or removing salt deposits have included

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maintaining the fractionator temperature high

enough to ensure the sublimation of all the salts
or, where this is not possible, water washing of
the tower. FCC feed desalting is also an option to
consider if long-term processing of heavy,
contaminated feeds is anticipated. However, the
use of salt dispersant additives can allow refiners
to avoid more costly means of FCC naphtha fractionation, and potentially avoid the practice of
water washing of the main fractionator.

Salt deposit formation

Ammonium chloride salt deposition is a problem
in FCC fractionator towers when sufficient
amounts of both ammonia and hydrogen chloride
are present. The formation of solid ammonium
chloride occurs when the salts precipitate from
the vapour phase. The deposition occurs when the
product of the partial pressures of the ammonia
and hydrogen chloride are greater than the stability constant (Kd) of ammonium chloride at the
system temperature.
NH3 (g) + HCl (g) NH4Cl (s)

Ammonium salts are highly water soluble, with

negligible solubility in hydrocarbons. Depending
on the level of reactants and the conditions inside
the tower, salts can deposit and accumulate at
temperatures above the water dewpoint. The
accumulated salts can cause severe restrictions in
the operation of the FCC. In addition, the ammonium chloride salts will readily absorb water. The
damp salts can set up extremely corrosive conditions on fractionator trays, piping, and exchanger
surfaces.

PTQ Q2 2001 1

over 90 per cent of the

current
pool
sulphur.
Therefore, reduction of FCC
naphtha sulphur content is
essential to ensure regulatory compliance.

Direct undercutting
Examination of a typical full
range (C5-220C) FCC naphtha composition shows that
Figure 1 Typical olefin and sulphur concentrations in FCC gasoline
most of the sulphur is
concentrated in the heavy
European Union specifications for gasoline call naphtha fraction. The majority of the olefins are
for a maximum of 30ppm sulphur content by found in the lighter naphtha fractions (Figure 1,
2005, with a maximum of 150ppm until that time. on previous page).
Germany is already pushing to achieve 10ppm
Since olefins have a higher octane value than
sulphur gasoline by 2003, and has introduced a the corresponding paraffins, it is desirable to
proposal to the European Union for sulphur- minimise the saturation of olefins. Therefore,
free fuels by 2007 [Nocca J L et al, The domino fractionation of the FCC naphtha followed by
interaction of refinery processes for gasoline quality hydrotreatment of the heaviest fraction allows the
attainment; NPRA Annual Meeting, March 2000].
refiner to remove most of the sulphur and miniIn the USA and Canada, gasoline sulphur mises the overall loss in octane. Further sulphur
content will be 30ppm maximum by 2005. To removal from the light naphtha fraction can be
meet this quality, pool gasoline sulphur will have accomplished by mercaptan sweetening.
to be reduced by more than 90 per cent compared
One route to fractionating FCC naphtha is to
to current levels [Billon A et al, A novel approach to install a heavy naphtha draw off the main fracattain new fuel specifications; European Refining tionator tower 15-20 per cent of the naphtha
Technology Conference, Paris, 22-24 November can be drawn off and hydrotreated. This is typi1999].
cally a minimal cost option for fractionating the
FCC naphtha makes up roughly 39 per cent of naphtha, and lessens the loading on the overhead
the US gasoline pool composition, but contributes condensing system. With limited capital available,
refiners may initially opt for this lower cost
option.
However, direct undercutting of the FCC naphtha results in a lower temperature in the upper
part of the main fractionator tower. If sufficient
levels of hydrogen chloride are present, the lower
tower temperature will result in deposition of
ammonium chloride in the top of the column
(Figure 2).

Atmospheric resid

Figure 2 Typical locations of salt fouling deposits in FCC

main fractionators

2 PTQ Q2 2001

Another refining practice that contributes to the

ammonium chloride problem is the economic
incentive to process atmospheric residue through
the FCC. Residue commonly contains inorganic
salts, primarily NaCl, which dissociates to Na and
Cl in the riser. The sodium primarily deposits on
the catalyst but the chloride exits the reactor in
the form of hydrogen chloride.
Imported residues and vacuum gas oils (VGO)

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can often contain high salt

concentrations due to seawater
contamination.
Since
high
concentrations of ammonia are
usually present in FCC overhead
systems, an increase in hydrogen
chloride is usually responsible
for driving conditions to the
point above the temperaturedissociation constant curve,
where deposition will occur.
Refiners may eventually be
forced to invest in capital
projects to meet the new gasoline regulations. Installation of
naphtha splitters or feed desul- Figure 3 The effect of higher polytropic head on compressor capacity
phurisation units will be
necessary. Direct undercutting of the FCC naph- are extremely hydroscopic, and will absorb water
tha may provide the lowest-cost option to meet even at temperatures well above the calculated
water dewpoints. Insufficient water washing or
short-term gasoline sulphur requirements.
poor distribution of water during washing can
leave behind damp salts.
Impact on FCC operations
Localised water condensation can occur due to
Salt deposition in the top of the fractionator
causes a variety of problems. The economic penal- top pumparound or cold reflux streams returning
ties can be quite large, including costs related to below the bulk dew point temperature. The result
off-spec products, reprocessing costs, lower can be very aggressive under-deposit corrosion of
the tower internals. The resulting corrosion byconversion and octane, and reduced feed rates.
products can add to the problem of plugged tray
and product draws as the corrosion by-products
Plugged trays and product draws
As salt deposits accumulate, they can gradually are dislodged by turbulence in the tower.
Typically, the shell and trays of FCC main fracplug the trays in the top section of the tower.
When this occurs, a gradual increase in P across tionator columns are constructed of carbon steel,
the top section will sometimes be observed. As 5 chrome, 410 stainless steel, or 316 stainless
the problem worsens, flooding of the top trays steel. Any of these materials is susceptible to high
will occur, evidenced by a rapid increase in P. corrosion rates due to chloride attack.
Gamma ray scans of the top section of the column
can confirm the presence of flooding and verify Loss of fractionation
The increase in P resulting from salt deposition
the location of the problem.
Salt deposits and associated corrosion byprod- can have a negative impact on the fractionation
ucts can cause partial or complete blockage of efficiency between gasoline and LCO. Typically,
product draws. Fouling of the top pumparound there should be a significant gap of 15C to 28C
exchangers is commonly reported. This can limit between gasoline and the LCO. This refers to the
the pumparound rate and heat removal from the debutanised gasoline 95 per cent volume point
tower. Several refineries have reported difficulty and the LCO 5 per cent volume point. This gap
in meeting gasoline Reid vapour pressure (RVP) should be monitored. A symptom of tray fouling
specifications due to fouled debutaniser reboiler may be indicated by random changes in the gap
exchangers. Other refiners have reported difficulty or by a permanent reduction in the gap.
in operating their stripper and C3/C4 splitter
An increase in tower pressure drop will also
towers.
increase the de-superheating (flash) zone pressure in the tower bottom. This requires a higher
Increased corrosion
bottom temperature to achieve the same amount
Ammonium chloride salt deposits, once formed, of LCO recovery. Directionally, higher bottom

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PTQ Q2 2001 3

temperature will cause increased fouling in the

main column slurry circuit.
Loss of compressor capacity

Any factor that increases the pressure drop across

the reactor and the compressor suction drum will
have a significant effect on the wet gas compressor capacity. As the P increases, the compressor
suction drum pressure decreases, causing a reduction in compressor volumetric flow. This
relationship is defined by the following polytropic
head equation. For an FCC operating at or near a
compressor limit, an increase in tower P will
result in either a reduction in unit feed rate or a
reduction in riser top temperature.
Figure 3 illustrates the effect of lowering
compressor suction drum pressure (P1) on the
compressor capacity. This is one reason why
many units have been revamped with structured
packing rather than trays in the main column, in
order to improve distillation by increasing the
number of theoretical stages at a lower pressure
drop.
Polytropic head equation:

coke burn and reduce the unit feed rate or reduce

the amount of residue in the feed.
Since salt forming chlorides often come into the
unit in residue feeds, this can have a serious
impact on the FCC economics. In addition, the
increased reactor pressure will directionally cause
a lower gasoline octane number.
An increase in reactor pressure also increases
delta coke. This generally imposes significant
economic penalties.

Avoiding salt deposition

Desalting

Minimising contamination of the FCC feed with

chlorides is an obvious first step in prevention of
salt fouling. Good desalting of the crude oil will
minimise the salt content of the residue. Some
refiners operate FCC feed desalters, especially
when processing imported feeds that can be
contaminated with seawater.
Measuring the sodium content of the residue is
a means of monitoring the effectiveness of desalting and the potential amount of contaminant
chloride.
Overhead temperature

where:
T1 = Inlet temperature, R
P2 = Discharge pressure, bar
P1 = Suction pressure, bar
n = Polytropic exponent
MW = Molecular weight
Zavg = Average compressibility factor
As seen from the equation, higher suction drum
pressure lowers the polytropic head. Each 68
mbar of increased wet gas suction pressure resulting from reduced pressure drop between the
regenerator and compressor suction drum
increases the compressor gas capacity by more
than 5 per cent [Final report, 1996 American
Petroleum Institute/National Petroleum Refiners
Association Survey of Refining Operations and
Product Quality, July 1997].

Refiners have observed deposition of ammonium

chloride when the column overhead temperature
is below about 135C. Others have reported no
problems when operating at temperatures greater
than 120C [Refining Process Services Inc/Process
Consulting Services Inc seminar, FCC Product
Recovery Systems; presented Houston, Texas, March
1998].

The formation of salt depends on the partial

pressure of the ammonia and chloride ion in the
tower. Usually, the minimum temperature
accepted is 5C above the theoretical salt deposition point calculated on the basis of a typical
composition of the feed.
Some refiners have tried to drive the salts overhead by temporarily increasing the column
overhead temperature. The goal of this is to cause
sublimation of the solid salt. This approach has
been used with mixed success.
Tower water washing

Air blower constraints

An increase in P across the main fractionator

increases the pressure in the reactor and in the
regenerator, increasing the compression ratio of
the main air blowers. This can significantly limit

4 PTQ Q2 2001

Tower washing is commonly done to remove

water-soluble salts. This is done by either injecting water into the top reflux or by lowering the
column overhead temperature enough to condense
liquid water on the trays. The water and dissolved

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salts are then removed through the naphtha or

LCO product draws. It is important to remove all
of the liquid water from the tower. Normal duration of the tower washings is between several
hours and over one day.
Tower water washing imposes significant costs
on FCC operations. During water washing, the
unit feed rates must normally be cut by as much
as 2030 per cent for at least several hours and
sometimes up to two days. During water washing,
naphtha and possibly LCO goes off-specification
and must be sent to slop, with potentially significant re-processing costs. In addition, water added
to the column may cause damage to the tower
internals.

Salt dispersant additives

Process chemical additives have been used in
numerous FCC units to control ammonium chloride deposition. The additives have proven to be
an effective alternative to tower water washing,
with minimal disruption of FCC operations.
Nalco/Exxon has developed application procedures and monitoring techniques to remove
deposits in the minimal amount of time.
The salt dispersant additives work by chemically
binding to the salt deposits, then physically lifting
them into the liquid phase, where natural turbulence carries them out of the system. The salts are
typically removed via the heavy naphtha or LCO
side draws.
The additives can be used in one of two ways:
Cleaning mode. In situations where the tower is
already severely fouled, the additives can be used
in a cleaning mode to disperse the salts and associated corrosion by-products out of the tower.
A high dosage of chemical is typically injected
for several days to the top reflux or pumparound
return line. The purpose is to quickly contact and
clean out existing solids. In this case, the
dislodged salts and corrosion debris are removed
from the tower via the heavy naphtha and/or LCO
product draw.
Consideration should be made of the impact of
the salts and solids on downstream equipment.
During cleaning of severely fouled systems, the
product streams may be sent to slops to minimise
the impact downstream.
Maintenance mode. In cases where there is a
chronic tendency to deposit salts in the tower, salt
dispersant additives can be used on a continuous
basis to maintain clean conditions inside the

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tower. When used in this manner, salts are

cleaned from the system as they form.
Salt dispersant additive performance can be
measured in a number of ways. Column P
trends are a common indicator of performance.
As the deposits are removed, better cut point
control
is achieved, and higher compressor
suction drum pressure is commonly observed.
Gamma scans of the upper part of the tower are
commonly used to confirm the location and severity of salt deposits. As the deposits are removed,
gamma scans can be used to confirm a return to
normal operation.

Case study
Texaco Pembroke

Salt dispersant additives can be used to both clean

towers and equipment that have already fouled
with salts, or they can be used to maintain clean
conditions as shown in the following example
from the Texaco Pembroke refinery. The example
shows how salt dispersant chemistry was used to
clean a severely fouled system, avoiding unit shutdowns and allowing increased residue processing
through the FCCU.
The feed to the FCCU is a mixture of VGO and
atmospheric residue. When economics dictate,
imported residue is charged to the FCCU.
As a result of a new side draw on the main fractionator, the top temperature was reduced by
approximately 30C. With a cooler top temperature the end point of the heavy cat naphtha (HCN)
was reduced. These modifications have resulted in
a reduction in the sulphur in gasoline to meet the
year 2000 specification of 150ppm pool sulphur.
The FCCU feed is not analysed for chlorides,
but since the majority of chlorides will be present
in salt water it was decided to analyse for sodium
to give an indirect indication of the amount of
chlorides in the feed.
Typical VGO feeds do not contain any significant quantities of sodium chlorides, since the
crude oil is treated via desalters. However, on
analysing the imported atmospheric residue the
sodium concentration was 20ppm, indicating at
least 20ppm of chlorides. With a VGO chloride
concentration of 1ppm, this resulted in a
combined feed chloride concentration of 5ppm.
The sodium in the feed was deposited on the
FCCU catalyst, which resulted in an increased
fresh catalyst addition rate (50 per cent) in order
to achieve the desired yield. The E-Cat results

PTQ Q2 2001 5

show the sodium levels increased from 0.29 wt%

to 0.55 wt%, even with the higher catalyst
additions.
As the fouling inside the FCCU main fractionator and the overhead system increased, the
separation in the top section of the column
became worse, resulting in heavier material being
carried overhead and the HCN end point specification harder to achieve. Heavy material would
carry overhead, causing instability and a small
feed rate reduction.
At the same time the wet gas compressor (WGC)
suction pressure began to fall, indicating that the
primary overhead exchanger was fouling. This
resulted in the WGC requiring more steam to
maintain the desired top temperature and the
governor position increasing. The increase in
governor position was essentially the point where
feed rate was reduced to bring the WGC governor
back on control. At this point a chemical injection
system was set up to inject the salt dispersant
additive into the overhead system and into the
reflux system. At the same time the overhead
exchangers were water washed one at a time, and
over a period of seven days the WGC suction pressure recovered, which enabled the feedrate to be
increased.
With the chemical being injected into the
column and overheads, the top column pressure
drop reduced to the design pressure drop. With
this reduction in pressure drop the separation
between HCN and HHCN improved and the
desired HCN end point was achieved.
Within two days of a recent startup the top
column pressure drop increased at a unit feedrate
of 80 per cent of design. A column scan was
carried out and confirmed that all the trays were
in position, there was no mechanical damage but
the top three trays were fouled and completely
full of liquid.
The reason for this sudden increase in fouling
was due to the rapid cooling of the column and
shifting of deposits from the top reflux/overheads
system back into the column. The salt dispersant
chemical was injected at a concentration of
20ppm and after four days the pressure drop had
reduced to normal levels and the feed rate
increased to 100 per cent of design. Subsequent
column gamma scans confirmed the complete
cleaning of the tower.
Application of the salt dispersant additive has
provided substantial benefits. Besides the opera-

6 PTQ Q2 2001

tional improvements previously described, the

additive has allowed the refinery to process the
desired amount of atmospheric residue and the
desired feed rates. Without the chemical, regular
water washing would have to take place with the
unit effectively shutdown for two to three days for
the duration of the water wash, since the refinery
has limited tankage to handle slops. The main
fractionator would be slumped and the column
water washed with all products off spec.
Had the salt fouling continued, then the column
would have to be water washed every three
months.

Benefits
Ammonium chloride salt deposition in FCC main
fractionator column internals is a common cause
of operating bottlenecks. Current trends in refinery operations to meet pending clean fuels
legislation mean that this problem will become
more widespread. Refiners, in the short term, will
look for the lowest cost gasoline post-treatment
desulphurisation schemes to ensure compliance.
Nalco/Exxon additives for removal and control
of ammonium chloride deposition have been used
with minimal impact on downstream operations.
Benefits of using the additives include improved
operations and reliability, increased conversion,
and higher unit throughput. The additives are a
cost-effective alternative to tower water washing.
Diagnostic tools such as gamma scans are a
useful method of trouble-shooting such problems,
and of verifying the effectiveness of a chemical
treatment programme. Cleanup of heavily fouled
trays has been accomplished in as little as three
days.
This article is based on a paper presented at the European
Refining Technology Conference, Rome, 13-15 November 2000.
David O Martin is senior product manager, refinery and fuels
management, with Nalco/Exxon Energy Chemicals of Fareham,
England, responsible for Europe, Africa and the Middle East.
Richard Allen is an FCC process engineer with Texaco Ltd, and is
based at the companys Pembroke refinery, South Wales.

LINKS
More articles from the following categories:
Corrosion/Fouling Control
Fluid Catalytic Cracking
Process Chemicals

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