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Technical

Paper

Control Of Salt-Initiated Corrosion In


Crude Unit Overhead Systems
Authors: James R. Rue and James G. Edmondson
selection, as well as unit design. The crude slate
Abstract processed and desalter operation will also have a
significant impact on the level of chloride and
The neutralization of acids in the crude unit over- other acids that require neutralization in the over-
head condensing system using ammonia or head system. Desalting efficiency is critical to lim-
organic amine neutralizers is standard practice. iting hydrolytic salts that enter the crude furnace
These neutralizers can be misapplied or recycled and produce HCl (hydrochloric acid). Caustic injec-
with water streams routed to the crude unit desal- tion is applied in some crude units to reduce over-
ters. As a result, corrosive chloride salts can form, head chlorides, but may not be practical where
causing severe fouling and corrosion of tower sodium concerns raise downstream issues for the
trays, overhead vapor lines, and condensers. fluid catalytic cracking unit, coker or other cata-
Several techniques have proven effective in miti- lytic units. Overhead water washing effectiveness
gating these problems. They include crude oil is dependent on proper volume and good distribu-
desalting, caustic injection for overhead chloride tion to force water into all areas prone to salting.
control, water washing, filming amines and more
recently, adding low base strength neutralizers to Unit design and operating conditions have a direct
control corrosive salt formation. bearing on where salt deposits form within the
system. Some exchanger designs have proven
The proper chemistry, effective monitoring tools, difficult to water wash and salt-related corrosion
and rapid response to upsets are needed for salt develops in localized areas. As an example, double
fouling and corrosion control. A detailed case his- drum design may result in salt formation in the
tory is presented highlighting application of these hot drum condensers, with no provision to remove
techniques. Elimination of lost production and salt deposits with a water wash. Salts can be
increased condenser life has resulted in reduced refluxed back to the distillation tower.
operating costs.
Effective corrosion control programs are being
Introduction applied where a history of salt fouling and related
corrosion has been experienced. Identification of
Fouling and corrosion from chloride salts have potential areas subject to salt fouling and under-
long been recognized as negative side effects of standing the limitations of existing corrosion con-
acid neutralization in the overhead condensing trol practices has been the key to success.
system of crude distillation units. Film-forming Application of filming inhibitors and LoSALT* neu-
corrosion inhibitors and organic amine neutraliz- tralizing amines has improved results in many of
ers are routinely applied to address this issue with these severe and challenging applications.
generally good performance.1
Many variables impact the potential for chloride
salt fouling and related corrosion. These variables
include chloride concentration, water washing
practices, filming inhibitor and neutralizing amine

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Corrosion Control Overview pend caustic addition when processing resid.
Caustic addition promotes coking and is therefore
Crude Oil Desalting a concern in the crude preheat train, atmospheric,
vacuum and coker heaters. Another significant
Effective crude oil desalting removes 90% to 99% concern in the coker is that caustic promotes
of the water soluble salts. Two stage desalting is foaming in the coke drums. These issues often
used by some refiners to increase salt removal cause refiners to limit caustic addition.
efficiency to the upper end of this range; however,
residual salt is often still present at levels which Overhead Water Washing
can lead to fouling and corrosion problems in the
overhead system. Many of the variables that Water wash addition to the overhead vapor line is
impact good crude oil desalting are well known by a common method often used to address salt-
the industry. 2 related fouling and corrosion. The most common
source of water wash is recirculation of the water
Opportunity crude oils have increased risk of cor- from the overhead receiver. Ammonium chloride
rosion since they are often higher in salt content and amine hydrochloride salts are very soluble in
and more difficult to desalt. Laboratory studies the overhead water. The goal of the water wash is
have confirmed a level of unextractable hydrolyz- to dilute the acids at the point of injection and to
able chloride present in several crude oils. This carry salts in a dilute solution.
work explained how atmospheric tower overhead
chloride levels are many times greater than salt Water washing can fail to achieve the desired
analysis by extraction techniques would indicate. results for a number of reasons. Good system
Units processing certain Arab, Cabinda and Dejno design is needed to assure adequate dispersion
crude blends have observed this for some time. and distribution. In order for water washing to
Even after double desalting, these crude oil blends successfully control fouling and corrosion, excel-
yield unacceptably high overhead chloride levels lent contact and mixing of the water with the gas
that range from 100 to 300 ppm (mg/L). 3,4 must be achieved. Spray nozzles or quills are
needed to promote dispersion in the vapor stream
Caustic Addition and to avoid erosion corrosion on overhead pip-
ing. Also, the volume of water injected should be
Caustic addition for overhead chloride control is above that needed to achieve water condensation
practiced by many crude unit operators. At typical at the point of injection and provide an excess of
crude unit furnace temperatures, calcium and liquid water. Further care should be taken to
magnesium chlorides can be hydrolyzed and con- assure separator vessels are adequately sized to
tribute to the HCl concentration. Caustic addition promote good separation of water and hydrocar-
helps convert these compounds to more ther- bon. This prevents reflux of water containing salt
mally stable sodium chloride, reducing the level of back to the crude column or downstream with the
HCl that vaporizes overhead. Feed of caustic is hydrocarbon product.
common in the 1 to 3 pound (0.45 to 1.36 kg) per
thousand barrel (ptb) range. Other critical caustic Many operating systems are not designed with
addition practices are documented in the litera- water wash, and capital costs to retrofit these
ture. 2,5 systems can be quite high. Also, salt fouling and
corrosion on hot exchangers of multiple drum sys-
In many systems, caustic addition rates in this tems require special consideration. The hot drum
range control the overhead water chloride levels is designed to operate well above the water dew-
to a range of 10 to 30 ppm (mg/L) . Experience has point. Water separation is not considered and
shown that the lower the chloride content, the water washing is impractical.
lower the corrosivity and salt fouling potential.
It has been industry’s experience that some
In some refineries, the addition of caustic is exchanger designs can prove difficult to effec-
restricted based on downstream operations. The tively water wash. In the exchangers, the water
level of sodium is most often a concern when distributes along different paths than do the liquid
atmospheric resid is processed at the Fluid Cata- hydrocarbons and condensing vapors. Water
lytic Cracking Unit (FCCU). Some refiners will sus- separation from the vapor stream leaves a portion
Page 2 TP1101en 0603
of the exchanger subject to localized salt buildup salt precipitation first occurs. These “saltpoint”
and corrosion. One refiner attempted to address calculations have shown great utility in predicting
this particular problem by tapping into the shell of the occurrence of deposition in overhead systems
the exchanger and placing a supplemental wash and in selecting traditional amines or low base
where salt buildup had been observed. This only strength neutralizing amines.8
provided marginal benefit as localized corrosion
moved to an intermediate point in the exchanger. Tramp Amines

Neutralizers Salt fouling and corrosion can be caused by


ammonia and amines present in the crude unit
Hydrochloric acid condensation in the overhead other than those used for neutralization. Possible
system causes severe strong acid attack if neu- sources of ammonia and amines are thermal deg-
tralization is not provided. Water dewpoint pH radation of crude oil, oil contamination, neutraliz-
values as low as 1.5 have been observed where ers in stripping stream when boiler condensate is
neutralizer feed was interrupted. Basic neutraliz- used, blow down from the alkanolamine unit and
ing compounds, such as ammonia and low stripped sour water used as desalter wash water.
molecular weight amines, are used to adjust the “Saltpoint” calculations can be used to determine
condensed water pH to near neutral (5.5 to 6.5), the potential contribution of these amines to salt
thereby reducing the corrosion potential. A poten- formation. Understanding which compound may
tial negative side effect of neutralizer or ammonia be present and its concentration is critical to
addition is that improper neutralizer selection can evaluation of its “saltpoint” and its impact on foul-
result in salt formation above the water dewpoint ing and corrosion.
causing either fouling or underdeposit corrosion.
Corrosion Inhibitors
Salts exist either as solids or low melting liquids,
depending upon the nature of the salt and tem- Surface active “filming” corrosion inhibitors can
perature of salt formation. Salts that are solid at reduce fouling and underdeposit corrosion caused
the temperature of salt precipitation have proven by ammonia or amine salts. This has been dem-
to be a greater risk of flow restriction and under- onstrated in the lab and field. There are several
deposit corrosion since they can agglomerate into possible modes of action. One theory is that the
thick salt layers. High general corrosion rates are filmer prevents adherence of salt to the equip-
often seen with liquid salts above the water dew- ment similar to the way that it prevents adher-
point. Liquid salts tend to be more corrosive than ence of corrosive aqueous phases. It has also
solid salts by providing more intimate contact of been shown that surface active compounds can
the metal surface and kinetics of electron transfer. adsorb onto the growing salt particles and dis-
In areas of high vapor velocity, acceleration of an perse them into a hydrocarbon phase. Many film-
erosion corrosion mechanism is often seen. This is ing compounds contain basic nitrogen
common in the vapor line and exchanger inlet functionality that can displace ammonia or amine
areas. Corrosivity of various amine salts was first in the crystal lattice and form oil-soluble salts,
discussed in 1990.6 thereby reducing the precipitation or deposition
potential of the problem amine.
In 1994, Edmondson and Lehrer introduced the
relationship of neutralizers with HCl in the vapor The effectiveness of filmers is generally lower for
phase.7 They found that different amine chloride salt corrosion than for aqueous corrosion. Since
salts had different condensation temperatures. the salt precursors are volatile and the filming
Furthermore, they found as the concentration of inhibitor is not, the filmer does not always distrib-
either the chloride or amine increased, so did the ute to areas subject to salting. The adsorption of
partial pressure in the vapor and the temperature filmers onto corroding surfaces is reduced at
at which the salt would form. Development of higher temperatures where salt formation is likely.
equilibrium vapor pressure data for various amine The deposition of salt shields the surface, prevent-
salts led to the introduction of the term “saltpoint,” ing adsorption of the filmer. Further, the salts of
and software development for its routine calcula- many neutralizing amines are viscous and adher-
tion. The “saltpoint” is the temperature at which ent, thus making it difficult for the detergent
TP1101EN 0603 Page 3
action of the filmer to displace the salt. If the salt Table 1: SEM-EDXA Analysis of Shell-Side Deposits
remains in contact with the surface for a signifi- Removed From The Failed Tube. The Smooth
Deposit Was Collected From A Non-Pitted Area
cant length of time, thick metal chloride and sul-
fide deposits are formed that further block the
metal surface from treatment. Pit Smooth
Element
(weight%) (weight %)
Case History Copper 31.0 24.1

A refiner operating a 40,000 barrel per day crude Nickel 32.6 35.0
unit had a history of short bundle life while proc- Sulfur 21.7 27.3
essing an Arab crude oil blend. The design was
such that the problem area was the first con- Iron 4.9 10.3
denser prior to the hot drum on a double drum Chlorine 3.4 1.3
overhead system. This condenser is constructed
of copper nickel (70/30) and is a vapor belt design. Aluminum 3.4 0.6
The vapor inlet temperature to the condenser was Barium 2.5 -
290°F (143.3°C) and the outlet was 200°F (93.3°C).
A water wash was used to eliminate the ammo- Silicon 0.6 0.9
nium chloride salts that form prior to the water Calcium - <0.5
dewpoint as a result of ammonia neutralization of
HCl and other acids. A filming amine was also Table 2: Semi-Quantitative SEM-EDXA Analysis Of Shell-
being fed for corrosion control. Side Deposits On The Non-Failed Tube.

Results were poor. The tube bundle had a history Blue Gold Black
of being replaced after only eight months of Element
(weight %) (weight %) (weight %)
operation. During the twenty-one months
between August 1994 and May 1996, the tube Copper 55.9 14.8 14.2
bundle was replaced three times and bypassed Nickel 11.7 54.6 43.4
twice to repair leaking tubes. Severe pitting and
general corrosion were seen throughout the con- Sulfur 30.2 28.5 38.4
denser. Also, weld repairs had been required on Iron 1.9 1.4 3.7
the overhead vapor line where severe thinning
was experienced. Chlorides from this Arabian Silicon <0.5 <0.5 -
crude slate, after a single stage desalter, were in Aluminum <0.5 <0.5 -
the range of 200 to 300 ppm (mg/L) in the over-
head water obtained from the hot drum. It was Potassium - - <0.5
clear that the high chlorides in the overhead was 1. Caustic injection to the desalted crude for
leading to salt-related corrosion and subsequent chloride control. Chlorides were brought under
tube failures.
control, and are now maintained in the 10 to
The high cost of corrosion was determined with 20 ppm (mg/L) range.
input from several groups within the refinery. 2. A low base strength neutralizer replaced the
Costs associated with the problem came from ammonia feed to the atmospheric tower over-
crude throughput reductions, frequent tube bun- head.
dle replacements, increased maintenance and
inspection costs. 3. The neutralizer injection point on the atmos-
pheric tower was moved from the reflux line to
GE Water & Process Technologies started a corro- the overhead vapor line.
sion control treatment program in April 1996. Over
4. Elimination of the overhead water wash. Due
the next year, several aspects of the program
were upgraded to improve performance. Key to high velocity and insufficient water, high
elements of the program included: corrosion rates were observed with the water
wash. At times, 50% naphtha was being recir-
culated.
Page 4 TP1101en 0603
5. Corrosion monitoring was upgraded with cou-
pon and corrosometer probes in several loca-
tions. This provided a means of collecting
information on both the corrosion rate and the
mechanism as well.

Initial results were disappointing, as tube failures


were experienced eight months into the program.
Six tubes were plugged at that time due to very
isolated and severe pitting attack. Long sections
of the copper nickel tubing were inspected and
only isolated areas near baffling showed the
aggressive corrosion. Most of the tube surface
had a thin sulfide scale that was dark blue, black
and gold in color with minor general corrosion
Figure 1: Shell-side surface of Tube 1E where there was a
observed under this scale. Table 1 shows deposit combination of blue, gold, and black deposit
results from the pitted and adjacent non-pitted
area. Chlorine was highest in the pitted area.
Table 2 provides the analysis of different-colored
sulfide scales found away from the pitted area.
Pictures of the tubes taken during failure analysis
are shown in Figures 1 through 4. During this early
phase of the program, periodic chloride spikes to
levels in excess of 100 ppm (mg/L) had been
observed. Ammonia from the vacuum tower over-
head application was also found to impact the
atmospheric tower from recycle via the desalter
wash water. Tube failures were experienced on
two separate occasions following significant
excursions. Amine and ammonium salts were
seen in the pitted areas.
“Saltpoint” calculations showed process side neu- Figure 2: Shell-side surface of Tube 1E after the deposit
tralizer would only exceed the water dewpoint of was removed using glass bead blasting. No
225°F (107.2°C) by a narrow margin when chlo- significant corrosion was found on this tube.
rides approached 100 ppm (mg/L). Another con-
cern was that the cold side fluid was cold crude
which could promote low skin temperature and
localized salt deposition. It was concluded that the
chloride excursions in combination with low tube
side temperature were the most likely factors con-
tributing to the localized corrosion.
Results improved once several additional program
upgrades were put into effect and chloride spikes
were eliminated. These included installation of a
spray nozzle at a secondary filming amine inject
-tion point at the condenser inlet. The goal was to
force more of the inhibitor solution into the vapor
phase and protect low flow areas where localized
pitting attack had been seen. Also, caustic soda
Figure 3: The failed region of Tube 4A where there was a
feed to the desalter wash water was initiated. The localized zone of severe pitting corrosion.

TP1101EN 0603 Page 5


following pH elevation of the desalter brine water,
additional amine recycle was detected and found
to be of significant benefit to program economics
while performance was maintained. Overhead
water analysis confirmed the level of amines de-
termined was over ten times greater than the level
applied at that time. The data in Table 3 shows the
level of both steam side and process neutralizing
amines, Amine A and Amine B, detected at the
time. Amine B has the greater oil solubility and
was reduced to a greater extent in the desalter
brine, indicating oil partitioning.
Feed of low base strength neutralizer on the
atmospheric tower overhead was substantially
Figure 4: Photomicrograph showing the microstructure reduced. At times the neutralizer feed on the vac-
observed at the external surface of Tube 4A uum side eliminated the need for further addition
where there were shallow, tunneling pits.
while pH control was achieved on the atmos-
pheric tower due to the amine recycle. This was
objective was to elevate the desalter brine pH
the result of higher solubility of the free amine in
from <4.0 to above 7.0. Oxygen from the surface
the oil phase following the pH increase in the
water was reacting with the sulfur compounds to
desalter brine. The application of an amine with a
depress the pH. Water chemistry of the surface
significant oil partitioning of the free base was
water is such that very little buffering is provided.
found to be a distinct advantage in this applica-
Corrosion in the brine piping had been observed
tion as program costs were reduced and salt for-
and this was reduced with pH elevation.
mation remained under good control.
After the secondary filmer injection, increased
filming inhibitor feedrate, elimination of ammonia Vacuum Atmos- Desalter Desalter
feed to the vacuum overhead and pH elevation at Ovhd. pheric Wash. Brine.
Amine
the desalters, no additional failures where ob- (ppm Ovhd.. (ppm (ppm (ppm
[mg/L]) [mg/L]) [mg/L]) [mg/L])
served. Carbon steel corrosion rates were consis-
tently less than 5 mpy. The copper/nickel tube Cyclo-
5 14 6 3
hexylamine
bundle was replaced with a carbon steel bundle at
a scheduled turnaround after two and a half Mono-
ethanola- 2 3 1 1
years of service, although it was reported to be fit mine
for further service and designated as a spare.
Amine A 78 59 31 18
Carbon steel was selected on the basis of im-
Amine B 290 116 123 17
proved corrosion protection, economics and the
projected future run length of the unit. The carbon Table 3: Water Analysis
steel bundle performed without incident over the
next year and corrosion rates continued low. At Conclusion
this point the unit was placed on stand-by status
for future use during turnarounds on the larger Salt fouling and related corrosion has been identi-
crude units. fied in many crude unit overheads. This can be a
concern on tower trays, top pump around
Ammonia and amine recycle from the desalter exchangers, the overhead vapor line and con-
wash water to the atmospheric tower overhead densers. Today, effective monitoring and control
was observed at this facility. As a result, the appli- programs are being applied to address these con-
cation of ammonia feed at the vacuum tower cerns. Several options are available to modify the
overhead was replaced with a low base strength "Saltpoint", disperse salts with filming amines
neutralizing amine. This was based on the obser- and/or provide a water wash. Monitoring program
vation that ammonia was present in deposits performance using computer simulation, thor-
where pitting corrosion caused tube failures. Also, ough analysis and inspection is essential to good
Page 6 TP1101en 0603
results. Proper application of treatment chemistry
and making the needed changes in corrosion con-
trol programs leads the way to reducing the cost
of corrosion.

References
1. J. R. Rue and D. P. Naeger, “Advances in Crude
Unit Corrosion Control,” CORROSION/87, paper
no. 199, (Houston, TX: NACE 1987)
2. Ara Bagdasarian, Jim Feather, Bob Hull, Ray
Stephensen and Russell Strong, “Crude Unit
Corrosion and Corrosion Control,” CORRO-
SION/96, paper no. 615, (Houston, TX: NACE
1996)
3. M. S. Binford, P. R. Hart, “The Impact of Desalt-
ing Opportunity Crudes on Corrosion Precur-
sors,” CORROSION/95, paper no. 343,
(Houston, TX: NACE 1995)
4. M. A. Dion, “Desalting “Opportunity Crudes,” “
1995 NPRA Annual Meeting, paper no. AM-95-
69, (Washington, D.C.)
5. R. D. Merrick and T. Auerbach, “Crude Unit
Overhead Corrosion Control,” Materials Per-
formance, September 1983
6. J. R. Rue and D. P. Naeger, “Cold Tower Aque-
ous Corrosion: Causes and Control, CORRO-
SION/87, paper no. 211 (Houston, TX: NACE
1987)
7. J. G. Edmondson and S. E. Lehrer, “Advances in
Neutralizing Amine Technology,” CORRO-
SION/94, paper 514, (Houston, TX: NACE 1994)
8. Danny Clarida, Jim Johnson, Marc McConnell,
and Rusty Strong, “Corrosion and Fouling Ex-
periences in Crude Units Using Low Base-
Strength Neutralizer,” Materials Performance,
July 1997

TP1101EN 0603 Page 7