3100 Crude Distillation Units

Authors: R.I. Piehl, Carol Ann Laughlin, D.J. (Don) Truax

Abstract
This section covers materials of construction and other controls used to minimize
corrosion in furnace tubes and transfer lines, atmospheric and vacuum columns,
column overhead systems, and other crude distillation facilities. Corrosive agents
include high-temperature H2S, naphthenic acids, and HCl.
Contents

Page

3110 General Information

3100-3

3111 Corrosive Constituents in Crude Oil

3112 Mechanisms of Crude Unit Corrosion
3120 Crude Unit Furnaces

3100-9

3121 Furnace Tube Corrosion

3122 Furnace Transfer Line Corrosion
3130 Corrosion in Columns

3100-18

3131 Atmospheric Column Corrosion

3132 Vacuum Column Corrosion
3140 Atmospheric Column Overhead System Corrosion

3100-21

3141 Causes of Corrosion

3142 Process Controls
3143 Desalting
3144 Caustic Injection
3145 Wash Water Recirculation
3146 Neutralization
3147 Target pH Range of 7.58.0
3148 Corrosion Inhibitors

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3149 Materials of Construction

3150 Monitoring the Corrosion Control System

3100-28

3151 Vacuum Column Overhead System Corrosion

3160 Other System Corrosion

3100-29

3161 Atmospheric Column Sidecut Stripper Corrosion

3162 Gasoline Rectifier Corrosion
3163 Corrosion in Piping and Valves
3164 Corrosion in Pumps
3165 Desalter Corrosion
3170 References

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3110 General Information

A large part of the corrosion encountered in petroleum refining can be attributed to
the nature of the crude oil being processed. Although the hydrocarbons that constitute the majority of the crude oils are essentially noncorrosive, all crudes contain
organic and inorganic impurities that may, under certain conditions, cause appreciable corrosion. Since crude distillation is the first major step in the refining of a
crude oil, all of these corrosive constituents are normally present in the crude unit.
Their effect on the corrosion of crude distillation equipment is discussed in this
section.

3111 Corrosive Constituents in Crude Oil

Sulfur Compounds
Crude oil sulfur content varies from as little as a few hundredths of one percent to
over five percent. While exceptions are frequent, typical sulfur contents of crudes
from various sources are roughly as follows:
United States

0.5 to 2%

Middle East

1 to 3%

Far East (Including Indonesia)

very low, often < 0.1%

Africa

0.2 to 1%

Venezuela

1 to 5%

In some crudes, sulfur exists in elemental form or as dissolved hydrogen sulfide.

Slaughter, West Texas crude oil contains 0.68 weight percent hydrogen sulfide, and
the gas from certain Wyoming sour crudes contains 6.45 volume percent H2S. These
cases may, however, be regarded as extreme. The greatest percentage of sulfur in
most crudes has been found to occur as organic sulfur compounds, of which
mercaptans and disulfides are the most common.

Inorganic Salts
As received by the refineries, all crude oils contain some quantity of inorganic salts,
such as chlorides of sodium, magnesium, and calcium, sulfates, and carbonates.
While these salts are sometimes found as distinct crystals in the crude, they most
commonly occur in aqueous solution, having dissolved in the water accompanying
the crude. The salt content of crude oils may vary from 2 pounds to 200 pounds per
thousand barrels (PTB), but as received by refineries most crudes contain less than
30 PTB. Crudes shipped over the water in tankers generally average 1015 PTB
higher in salt content than those transported by pipeline.

Organic Acids
Various types of organic acids are found in crude oils. In the case of a few crudes,
they may exist in quantities large enough to constitute a serious corrosion problem
during processing. Of these, naphthenic acids are the most common. Crude oils
containing large quantities of naphthenic acid come from many locations, including

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California (Midway - Sunset, Kern), Venezuela (Merey, Lagotreco, Bachequero),

Sumatra, the North Sea (Alba, Griffin), West Africa (Cabinda, Forcados, Qua Iboe,
Escravos), and the Gulf of Mexico (main pass 299, Green Canyon). Highly naphthenic crudes likely to cause corrosion during processing are characterized by high
neutralization numbers of the heavier petroleum fractions.

Other Corrosive Constituents

Organic nitrogen compounds are found, to some extent, in all crude oils. These
compounds are noncorrosive as they exist in the crude, and are sufficiently
temperature-stable that they do not appreciably decompose during crude distillation. Although these nitrogen compounds are not a significant factor in crude unit
corrosion, they can decompose and cause corrosion in downstream catalytic
processes.
Certain metallo-organic compounds are also found in crude oil. Vanadium
compounds are particularly important in terms of corrosion. They do not contribute
to process-side corrosion in crude units. However, when vanadium-containing oils
are burned as furnace fuel, vanadium pentoxide is formed as a product of combustion. Vanadium pentoxide, as a major component of the fuel ash, can greatly accelerate the corrosion of tube supports and other furnace hardware which operate at
temperatures above the point where the fuel ash becomes molten (1200F1300F).

3112 Mechanisms of Crude Unit Corrosion

Areas of crude distillation units particularly susceptible to corrosion are shown in
Figure 3100-1. This section discusses the specific mechanisms of greatest concern
in crude units.

Sulfur Corrosion
Hydrogen sulfide is corrosive to carbon steel at temperatures above 500F and may
also contribute to corrosion and/or stress corrosion cracking at lower temperatures
in the presence of liquid water. Since most crudes contain little dissolved hydrogen
sulfide, it might be concluded that corrosion due to sulfur compounds should not be
particularly serious in crude distillation units. Unfortunately, many of the commonly
occurring sulfur compounds thermally decompose on heating to liberate hydrogen
sulfide. It is this liberated H2S that is responsible for most high temperature crude
unit corrosion in the form of high temperature H2S corrosion (also called
sulfidation). [1]
High Temperature H2S Corrosion (Sulfidation). The degree to which the sulfur
compounds of various crudes decompose to liberate hydrogen sulfide is shown in
Figure 3100-2. These data were obtained by a laboratory test involving heating the
crude sample at a controlled rate and measuring the quantity of hydrogen sulfide
evolved as a function of temperature. It is obvious from these curves that the
different varieties of crude oil vary significantly in the rate at which hydrogen
sulfide is evolved. While not apparent from the data, different crudes from the same
general area may differ widely in H2S evolution characteristics. This is particularly
true in the case of Arabian crudes. Imported crudes, as received at domestic

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Fig. 3100-1 Corrosion Mechanisms in Crude Distillation Units

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refineries, may also vary in hydrogen sulfide evolution as a function of their having
been stabilized prior to shipment.
Fig. 3100-2 Hydrogen Sulfide Evolution from Crude Oils, Chevron Proprietary Test Data

Since hydrogen sulfide is responsible for nearly all of the corrosion caused by sulfur
compounds, it is possible to obtain some measure of the corrosivity of a crude
oil by evaluating its tendency to evolve H2S upon being heated. For example,
Figure 3100-2 suggests that Santa Maria crude would be far more corrosive at any
temperature than Kettleman Waxy, and anyone familiar with the processing of these
two crudes would agree.
It is important to recognize that the hydrogen sulfide evolution test is a far better
criterion of corrosivity than the sulfur content of the crude. Because sulfur
compounds differ widely in resistance to thermal decomposition, it is not unusual to
find high sulfur crudes that are less corrosive than crudes containing only a fraction
as much sulfur. Results of hydrogen sulfide evolution tests on specific crudes may
be obtained from CRTC Materials and Equipment Engineering if an interpretation
of significance is desired; otherwise, directly from CRTC Process Planning.

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Wet H2S Cracking. At lower temperatures, where liquid water is present, wet H 2S
cracking is a potential concern. In crude units, such cracking is possible in the
column overhead and light ends systems. Refer to Section 450 of the Corrosion
Prevention and Metallurgy Manual for guidelines on addressing wet H2S cracking
concerns.

Corrosion by Inorganic Salts

The quantity of inorganic salts present in a crude oil varies widely, depending on the
composition of the brine from the oil well, the emulsification characteristics of the
crude, the method of transportation and the time allowed during storage for settlement and separation of the water phase.
The principal ingredients in this entrained water phase are the chloride, sulfate, and
carbonate salts of sodium, magnesium, and calcium.
Dissolved or particulate salts in the crude may cause plugging of feed heat exchange
equipment. Hot brine may also corrode the bottom of desalter vessels and desalter
effluent water piping.
However, the most damaging effect of these salts results from the tendency of the
chlorides to hydrolyze (react with water) at elevated temperatures to form hydrogen
chloride (HCl). It is generally believed that magnesium and calcium chlorides
hydrolyze readily, while sodium chloride does not.
In the crude distillation unit, hydrogen chloride is formed primarily in the atmospheric and vacuum furnaces. While there is currently no evidence to indicate that it
contributes to corrosion in either the furnaces in which it is formed or the hotter
parts of the columns which it subsequently enters, the HCl ultimately finds its way
into the overhead system of both the atmospheric and vacuum columns, where it is
absorbed in the condensing water, forming highly corrosive hydrochloric acid.

Corrosion by Organic Acids

As stated previously, the organic acids present in crude oil are largely naphthenic in
nature, being based on a saturated ring structure. These acids remain largely
unchanged during crude unit processing since temperatures of 750900F are
needed for acid decomposition. While only a small amount of thermal decomposition occurs in a crude unit, naphthenic acids decompose and neutralization numbers
and corrosion drop to nil in higher temperature downstream units such as thermal
and catalytic cracking units. [6]
Because most of the commonly occurring naphthenic acids are relatively high in
molecular weight, they are seldom found in appreciable quantities in the lighter
products from the crude unit. In those crude oils containing appreciable quantities of
naphthenic acids, it is usually found that high neutralization numbers can occur in
the entire VGO range (6501000F true boiling point (TBP)), where the acids are
concentrated due to distillation.
Naphthenic acid is a collective name for the various organic acids present in some
crudes. The acidity of a crude, called neutralization number, is measured by titration
with KOH. ASTM D-664, which uses potentiometric titration, is the most

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commonly used test. The test estimates two values: total acid number (TAN) and
strong acid number. The neutralization number is the total acid number minus the
strong acid number. As most crudes do not contain strong acid, the TAN is often
equivalent to the neutralization number.
Naphthenic acids cause corrosion because they convert normally protective iron
sulfide into oil-soluble iron naphthenate. The acid may dissolve the iron sulfide
scale entirely or only partially, leaving a poorly adherent material which is readily
stripped off by high velocities or turbulence. There is a competition between H2S
forming the scale and naphthenic acid dissolving it. At high neut numbers, any
sulfide scale present is dissolved and corrosion occurs. See References [5], [6], and
[7] for an in-depth discussion of naphthenic acid corrosion.
As may be expected with any corrosive constituent, the degree of corrosion encountered with naphthenic acids will be higher in those areas where the acid is allowed
to concentrate. In a crude unit, the areas of most severe naphthenic acid corrosion
are usually in those parts of the columns (particularly the vacuum column) where
the acids become concentrated by distillation.
The potential for naphthenic acid corrosion is largely dependent on neut number
(processing crudes with high neut numbers results in more corrosion). Previously
published thresholds for corrosion were reliable for California crudes, but recent
experience has shown the threshold may be different for other crudes.
Some general guidelines are as follows:

At low velocities, corrosion with California crudes has not been significant if
the neut number for the hydrocarbon fraction is below 1.5 mg/gm.

At high velocities (>100fps, like transfer lines, furnace tube return bends, outlet
headers), corrosion has been observed at neut numbers as low as 0.3 mg/gm.

These neut number thresholds do not hold true for all crudes. Some recent
examples of corrosion are:

A Chevron plant processing Venezuelan crude with a whole neut number

of 0.40.5 experienced corrosion in the light gas oil system where the neut
number was only 0.30.6.
Another unit had atmospheric furnace outlet header and transfer line corrosion while processing West African crude blends with whole crude neut
numbers less than 0.5.
A third Company unit had corrosion of vacuum column packing in the
overflash area, after processing North Sea and West African crudes. Neut
numbers were not recorded during the time when corrosion occurred, but
are believed to be less than 1.5 in draw streams.

In conclusion, we are still learning more about naphthenic acid corrosion. If you are
processing a crude with no previous experience, contact CRTC Materials and
Equipment Engineering for up-to-date advice. Assume that a crude with any naphthenic acid is potentially corrosive.

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The practical identification of naphthenic acid corrosion is usually based on the

following factors:

The appearance of naphthenic acid corrosion is highly characteristic, being

typified by channeling, grooving, and the absence of corrosion products. Such
corrosion is also highly sensitive to the effect of liquid velocity.

Unlike sulfur corrosion, naphthenic acid corrosion is no less a problem for

chromium steels such as 46% Cr and 12% Cr than for carbon steel. Under
certain circumstances this may also be true of Type 304L stainless steel. The
key to naphthenic acid corrosion resistance is stainless steel with molybdenum
(Mo) content greater than 2.5%. Type 316L stainless steel can contain
2.03.0% Mo. In the past, 316L was supplied with Mo contents in the middle
of the acceptable range, so it had satisfactory resistance to naphthenic acids.
Today, with improved steel making process control, 316L typically has Mo
contents near the lower bound, which is insufficient for corrosion resistance. To
ensure resistance today, 317L (3.04.0% Mo) is usually ordered, especially for
severe services such as furnace transfer lines and structured packing. 317L
cladding can be more cost effective than solid stainless steel for diameters
above 6 inches.

Naphthenic acid corrosion can occur at temperatures as low as 350F. Sulfur

corrosion does not occur below 500F, under dry conditions. For this reason,
corrosion occurring in the 350F500F range is probably caused by naphthenic acids.

A phosphorus-based corrosion inhibitor is being used on a trial basis at Pascagoula. Along with determining its effectiveness against naphthenic acid corrosion, the effect of phosphorus on fixed bed catalyst will be monitored. Contact
Materials and Equipment Engineering at CRTC for more information.

Summary of Corrosion Mechanisms and Control

Figure 3100-3 briefly summarizes the corrosives in crude oil, why corrosion occurs,
where it is likely to be found, and methods of control. Figures 3100-4 through
3100-6 show the parts of the unit where each type of corrosion is likely to occur.

3120 Crude Unit Furnaces

3121 Furnace Tube Corrosion
High Temperature H2S Corrosion (Sulfidation)
Most furnace tube corrosion in crude units is caused by hydrogen sulfide. The
severity of such corrosion is determined, primarily, by temperature and by the
degree to which H2S will be liberated from the crude during heating.
Laboratory data on the hydrogen sulfide evolution characteristics of several crudes
are shown in Figure 3100-2. The carbon steel furnace tube corrosion rates caused by
some of these crudes are given in Figure 3100-7. It will be noted that, for the three

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Fig. 3100-3 Corrosives in Crude Oil

Corrosion Control
Corrosive in
Crude

Why Corrosion Occurs

Neutralize

Yes (NH3,
neutralizing
amines)

Wash water
recirculation
also important

Inhibit

Magnesium chloride
and calcium chloride
decompose on heating
to form HCl

Occurs where HCl and

liquid water are
present (typically
column overhead
systems)

Monel
Cupro-Nickel
Admiralty
Carbon Steel

They thermally decompose to form H2S

Over 500F metal

temperature. Rate
depends on temperature and H2S concentration

300 Series SS
12% Cr
9% Cr
7% Cr
5% Cr
Carbon Steel

No

No

They are present in

some crudes and go
through the unit
unchanged

Over 350F, and where

neutralization number
is over 1.5, especially
in high velocity turbulent areas (see text)

317 & 317L

316 & 316L (>2.5%
Mo)
Other 300 Series
Carbon Steel

No

On trial basis at
Pascagoula. Contact
MEEU for current
information.

Salts
(HCl)

Sulfur
Compounds
(H2S)

Naphthenic
Acids

Upgrade Alloy
(Best to Worst)

Where Corrosion
Occurs

No

Fig. 3100-4 Typical Areas Susceptible to H2S Corrosion in Crude Units

Atmospheric
Column
Vacuum
Column

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Fig. 3100-5 Typical Areas in Crude Units Susceptible to Naphthenic Acid Corrosion

Atmospheric
Column
Vacuum
Column

Fig. 3100-6 Typical Areas in Crude Units Susceptible to HCI Corrosion

Atmospheric
Column

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crudes on which both corrosion and H2S evolution data are given, a direct relationship exists between these two variables. A quantitative relationship between H2S
evolution, temperature, and corrosion rate is given in Figure 3100-8. At the H2S
levels typically found in crude units, metal temperature is the most important variable affecting corrosion.
While the corrosion data in Figures 3100-7 and 3100-8 are correlated with stock
temperature, the actual rate of attack on furnace tubes is greatly influenced by the
temperature of the tube wall. As might be expected from the corrosion rate curves,
attack on furnace tubes is highly dependent on temperature distribution in the
furnace. It is not unusual to find accelerated attack at hot spots on tubes, and a high
eccentricity factor resulting from preferential corrosion on the fired side of the tube,
as shown in Figure 3100-9. It does not necessarily require extreme localized overheating to create a situation in which essentially all of the corrosion occurs on the
fired side of a radiant tube. As a rule of thumb, furnace tube corrosion rates double
for each 35F to 40F increase in temperature.
Fig. 3100-7 Corrosion of Carbon Steel Furnace Tubes by Various Crude Oils

Proper interpretation of the corrosion rate graphs requires some understanding of

what the indicated temperatures mean. Actual corrosion rates are determined by
metal temperature, not the temperature of the process fluid. For most plant equipment (columns, piping, etc.), the two temperatures are the same and corrosion rates
could be plotted as a function of either one. However, this is not true of furnaces.
Here, the metal temperature is considerably higher than stock temperature. To be

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Fig. 3100-8 H2S Corrosion of Carbon Steel Furnace Tubes

Fig. 3100-9 Furnace Tube Failure as the Result of Preferential Corrosion on the Fired Side

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technically correct, furnace tube corrosion rates should be plotted as a function of

metal temperature, not stock temperature. But because we generally do not know
the metal temperature, we plot corrosion rates as a function of stock temperature.
Recognize that a given stock temperature will show a higher corrosion rate on a
furnace tube plot than on a plot used for column corrosion rates. In other words, the
corrosion rate at 600F metal temperature might be plotted at 500F stock temperature. The amount of temperature shift in the curves is equal to the difference
between stock and metal temperatures. We commonly assume this to be on the order
of 100F.
Carbon steel tubes are often used for the convection section of the atmospheric
furnace. While this is often adequate, process and/or design changes can lead to
convection section corrosion. For instance, switching from bare to finned tubes to
improve heat transfer in the convection section can also promote high temperature
sulfidation. If such changes are anticipated, consider using 5Cr convection tubes, as
inspecting convection tubes for damage is difficult.
For radiant section tubes, carbon steel is only suitable when processing low H2S
crude at relatively low temperatures. Corrosion rates for 5-9%Cr tubes can be estimated by shifting the curves in Figures 3100-7 and 3100-8 upward in temperature.
Shift the curves up by 150F for 5Cr, 50F more for 7Cr, and another 50F for 9Cr.
Where corrosion of carbon steel is excessive, substantial benefit can be obtained
through the use of the chromium steels as long as the crudes being processed are not
high in naphthenic acids. The most commonly used material is 5% Cr - % Mo
steel which has been found adequate in all but the most severe conditions. For the
hottest parts of furnaces that handle extremely sour crudes, 7% or 9% Cr steels are
sometimes required.

Naphthenic Acid Corrosion

Furnace tube corrosion by naphthenic acids has increased greatly during recent
years, because our refineries are processing more San Joaquin Valley SJV and
other naphthenic crudes. One of the early case histories came from a unit feeding
Midway Special (California) Crude. Here, 46% Cr furnace tubes suffered corrosion where stock temperatures exceeded 700F. It was felt that attack was due to
naphthenic acids, because the corrosion of this material was much higher in this
environment than it was in a higher sulfur but low naphthenic Arabian Crude environment. This is illustrated in Figure 3100-10. Additionally, the corrosion of both
carbon steel and 4-6% Cr showed the washed out effect characteristic of naphthenic acid corrosion (see Figure 3100-11).
Residuum stripper units at both Richmond and El Segundo Refineries have suffered
naphthenic acid corrosion of 5, 7, and 9% Cr tubes. Corrosion took the form of
wash-outs at the outlet ends of the last tube pass.
Three factors cause naphthenic acid corrosion to occur near the furnace outlets.
First, temperatures are highest there. Second, fluid velocities are highest at that
point, owing to vaporization of the lighter constituents in the crude. Third, vaporization of the lighter constituents causes the naphthenic acids to concentrate in the
unvaporized liquid because the acids tend to have high boiling points. It should be

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Fig. 3100-10 Furnace Tube Corrosion by Crudes Containing Naphthenic Acids and
Evolving H2S

noted here that naphthenic acid corrosion is a liquid phase phenomenon. In a twophase system, it is the liquid phase that is corrosive. Corrosion can also occur in the
vapor if mist or liquid droplets are present.
Some crude units require higher alloys than the 5-9% Cr steels for furnace tubes
when processing the very highly naphthenic crudes like SJV. Better materials, in
order of increasing corrosion resistance, are the 18-8 stainless steels (Types 304,
304L, 347), 16-13-3 Cr-Ni-Mo stainless (316 and 316L), the slightly higher alloyed
317 and 317L Cr-Ni-Mo stainless steels, and Inconel 625. The exact service limits
for these materials, in terms of temperature and neutralization number, have not yet
been established. Choice of furnace tube materials for high-naphthenic service is
best made after reviewing field experience of various materials in the most similar
crude service.
When selecting stainless steel furnace tube materials, the possibility of polythionic
acid stress corrosion cracking should also be considered. See the Corrosion Prevention and Metallurgy Manual, Volume 1, Section 400 for a detailed discussion of this
phenomenon. When considering both naphthenic and polythionic attack at the same

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Fig. 3100-11 Effect of Naphthenic Acid Corrosion on a Carbon Steel Furnace Tube

time, Type 347 stainless may be adequate if naphthenic acid corrosion is mild; this
alloy has the best resistance to sensitization and polythionic acid attack. If a
molybdenum-containing grade is needed for naphthenic resistance, use Type 316L
(2.5% Mo min) or 317L. These materials may sensitize in time. To avoid eventual
polythionic attack, it is important to minimize the tubes exposure to water and
oxygen. In some cases, plants utilize a carbonate wash procedure and dehumidifiers
during the shutdown process.

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Naphthenic acid corrosion is an extremely complicated subject. References [5], [6],

and [7] present the most comprehensive discussion of the subject.
In the preceding discussion, no distinction has been made between atmospheric and
vacuum furnaces. The same general corrosion considerations are true in both
furnaces. The primary difference is that somewhat higher corrosion rates can
usually be expected in the vacuum furnace because of higher temperatures.

3122 Furnace Transfer Line Corrosion

Like furnace tubes, transfer lines may be subject to corrosion by either hydrogen
sulfide or naphthenic acids. H2S corrosion of a transfer line which is not externally
heated will be lower than that of a furnace tube of the same material operating at the
same stock temperature. Because metal wall temperatures are relatively uniform,
transfer lines will not show the highly eccentric corrosion commonly found in
furnace tubes as a result of differential temperatures. However, with highly naphthenic crudes, transfer line corrosion may be greatly influenced by turbulence.
Localized attack may occur at welds, bends, and particularly at tees where the pressure drop in the line results in sudden vaporization (flashing) of the hydrocarbons
and, hence, extreme turbulence.
Carbon steel transfer lines may show adequate corrosion resistance when processing
the milder crudes at relatively low transfer line temperatures. The 5% Cr steel is a
common transfer line material and generally performs well in sour crude service.
However, this alloy does have certain limitations. It is not likely to be satisfactory in
plants feeding highly naphthenic crudes. And in Middle East crude service, 5% Cr
steel may experience H2S corrosion if transfer line temperatures approach the 750F
to 800F level.
Another disadvantage of 5% Cr steel is difficulty of fabrication. Welds require
preheat and postweld heat treatment to avoid cracks during welding and to ensure
good mechanical properties in the weldment.
Type 304 stainless has been used for transfer lines in the past. It has better resistance to H2S and naphthenic acid corrosion than 5% Cr, and the installed cost is
often lower than 5% Cr. In most cases, performance has been excellent. However,
Type 304 will sensitize from the heat of welding, or from prolonged exposure to
operating temperatures above about 700F. This renders the material susceptible to
polythionic acid stress corrosion cracking during shutdowns. The incidence of such
failures has been low, but some have occurred. This has led to the use of stabilized
grades of stainless such as Type 347 or thermally stabilized Type 321 (heat treated
at 1650F after welding) in place of 304.
Units handling highly naphthenic crudes may experience localized corrosion of the
18-8 stainless steels (Types 304, 304L, 321, 347) at points of high velocity or turbulence. Bends (especially miters), tees, and thermowells have been common sites for
corrosion. Accelerated attack has also occurred downstream of thermowells and at
pass control valves at the furnace outlet. Localized attack like this is difficult to
predict. Several crude units have upgraded the entire transfer line to 316L or 317L
because of the inability to predict where the next leak might occur.

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When low-carbon grades of stainless steel such as 316L and 317L are used for
transfer lines, the possibility of their sensitizing in service must be considered. If the
line operates above about 700F, sensitization is likely and limiting contact with air
and water is critical. If the line must be opened to the atmosphere, carbonate
washing is desirable to minimize the chance of polythionic acid cracking.

3130 Corrosion in Columns

3131 Atmospheric Column Corrosion
Most corrosion encountered in an atmospheric column is caused by corrosives
formed in the atmospheric furnace, including hydrogen sulfide and hydrochloric
acid. The major concern is the nature and control of corrosion caused by the presence of hydrogen sulfide. Hydrochloric acid can cause considerable damage to the
upper part of the atmospheric column. This will be discussed in Section 3140.
Naphthenic acids are seldom found to cause corrosion in the atmospheric column
because the acids do not concentrate at typical atmospheric column temperatures.
It is a general rule that dry sulfur corrosion, or, more properly, hydrogen sulfide
corrosion, occurs at the maximum rate in the flash zone. This is to be expected,
since temperature, H2S concentration, and turbulence are at a maximum in this area.
Within the flash zone itself, corrosion of carbon steel is usually severe, except when
processing an extremely mild crude at relatively low temperatures. Corrosion may
be particularly severe at points of high turbulence or direct impingement against the
metal. Control of such corrosion is usually accomplished with a lining or cladding
of Type 405 or Type 410S steel (12% Cr). Types 304, 321, or 347 stainless steel,
while completely adequate in this location, are seldom required.
Above the flash zone, temperatures progressively decrease in an upward direction
through the column. This drop in temperature is accompanied by a decrease in
hydrogen sulfide corrosion. Corrosion is possible wherever temperatures exceed
500F, but significant corrosion usually does not occur below 575F.
Figure 3100-12 shows typical column corrosion rates as a function of H2S concentration and temperature. These data apply only to the part of the column above
the flash zone. Within the flash zone, corrosion rates will be higher than the curves
predict, due to turbulence. Below the flash zone, H2S content is both low and
impossible to determine, so these correlation curves cannot be used. Figure 3100-12
is equally applicable to vacuum columns, but only when naphthenic acid concentrations are low. When using Figure 3100-12, H2S concentration can be calculated
from the H2S evolution curve for the crude in question.
Below the flash zone, in the stripping section, corrosion rates tend to decrease
because the hydrogen sulfide is being stripped out of the oil and swept upward in
the column. Where bottoms temperatures are below about 650F, carbon steel has
generally proven adequate for the stripping section and bottom head. Above 650F
bottoms temperature, carbon steel may corrode at high rates, and alloy protection is
often required (see Figure 3100-13). This is presumed to be the result of the organic

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Fig. 3100-12 Typical H2S Corrosion Rates Above the Flash Zone in Crude Columns

Fig. 3100-13 Corrosion of Crude Column Bottom Heads

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sulfur compounds in the oil continuing to decompose and liberate fresh hydrogen
sulfide. Where this has occurred, it is typically found that the bottom head corrodes
more rapidly than the column shell in the stripping section area. H2S corrosion can
also occur on the reduced crude side of bottoms exchangers.
It is interesting that the corrosion rates in the flash zone may be increased significantly with any given crude by increasing the outlet temperature of the atmospheric
furnace. This results in a higher flash zone temperature, as well as an increase in
evolved H2S. A secondary result is that because of higher H2S concentrations the
rate of corrosion within the entire column will be raised.
The relative order of corrosion resistance of various alloys in the atmospheric
column is also important. While carbon steel is subject to corrosion in varying
degrees in the flash zone area, it usually has adequate resistance in most other areas
of the column. The chromium steels and chrome-nickel stainless steels are usually
good. Trays and strip lining of 12% Cr steel are necessary above the flash zone
when processing crudes such as Arabian Light which evolve high amounts of H2S.
Nonferrous materials such as Monel and the copper-base alloys will be severely
corroded in any part of the column where temperatures exceed about 500F.
Historically, little naphthenic acid corrosion has been experienced in atmospheric
columns. But some danger of naphthenic acid attack may exist in the atmospheric
columns of single stage crude units. Conditions favoring its occurrence are highly
naphthenic crude feeds, and high transfer line temperatures (over 700F). Under
these conditions, the hottest sidecuts could contain enough naphthenic acids to be
corrosive. Naphthenic acid corrosion is covered in Section 3132.

3132 Vacuum Column Corrosion

Since hydrogen sulfide is released from the crude oil in both the atmospheric and
vacuum furnaces, the same general problem of H2S corrosion exists in atmospheric
and vacuum columns. In either instance severity of corrosion depends both on operating temperatures and on the characteristics of the crude oil being processed. In
general, the methods of H2S corrosion control are similar for both atmospheric and
vacuum columns.
Only for extremely mild crudes and low column temperatures is carbon steel
completely acceptable in vacuum column service. In most cases, alloy lining or
cladding is required, at least in the flash zone. With extremely sour crudes, considerably more alloy protection may be needed. With Middle East crudes, for example,
alloy cladding and trays are needed wherever temperatures exceed 600F. The
12% Cr steels (such as Types 405 and 410S) provide almost complete resistance to
hydrogen sulfide corrosion under vacuum column conditions.
In most naphthenic crudes, the acidic constituents are found primarily in the gas oil
and light lubricating oil fractions, and are chemically related to the purely hydrocarbon components of these fractions. During crude distillation, the naphthenic
acids will, in most cases, tend to concentrate within the vacuum column above the
feed tray. The most severe attack is often confined to several trays. Severe

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naphthenic acid corrosion may ultimately require alloy protection throughout the
column.
Unlike the atmospheric column, the vacuum column itself may be subject to severe
naphthenic acid attack when highly naphthenic crudes are being processed. Such
corrosion is typified by sharp-edged channels and grooves in areas of high fluid
velocity and the absence of corrosion products (because most metal naphthenates
are oil-soluble). Packing is particularly susceptible. Company units have seen structured packing corrode in columns where sidecut neut numbers were believed to be
well below 1.5.
For crude oils high in naphthenic acid, it is necessary in most cases to protect the
vacuum column with Type 316L (> 2.5% Mo) or 317L stainless steel. The extent of
protection depends on the distribution of naphthenic acids within the column.
Alloys less expensive than Type 316L stainless steel, such as Types 304L, 321, and
347 are an improvement over carbon steel in such environments, but usually do not
provide long enough lives.
Company experience has shown that naphthenic acid corrosion is seldom significant below about 350F. At higher temperatures, naphthenic acid attack may be
expected if the neutralization number of the sidecut stream exceeds 1.5 mg potassium hydroxide (KOH) per gram.
On rare occasions, vacuum column top heads have suffered corrosion at temperatures above the boiling point of water but below 350F. This temperature range is
too high for hydrochloric acid corrosion, and too low for naphthenic acid attack.
Although this corrosion has occurred in plants processing naphthenic crudes, the
appearance of corrosion is smooth, unlike typical naphthenic acid corrosion. The
best current theory is that such corrosion is due to other acidic organic compounds,
like phenols, and is possibly accelerated by the presence of chlorides [6]. When this
type of corrosion is encountered, the remedy has been to line the affected areas with
Type 316L stainless. Neutralization is not an effective remedial measure.

3140 Atmospheric Column Overhead System Corrosion

3141 Causes of Corrosion
Corrosion Control Philosophy
Chevron developed effective technology to prevent overhead system corrosion in
the early 1970s and incorporated that technology into the crude units built after that
time. The concept involves operating the top of the atmospheric column hot enough
to keep potential corrosives in a harmless vapor state (staying above the water
dewpoint, usually 270F minimum) and quenching and water saturating the overhead vapors in the pipe between the column and the first condenser with alkaline
recycle water (recycle water with neutralizer added). This avoids neutralizer salt
sublimation, the low pH initial condensate, and the even lower pH condensate due
to partial water re-evaporation. Recycling water with neutralized salts also buffers
the condensate from the overhead stream and greatly stabilizes pH. With this

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system, carbon steel corrosion control simply requires adequate water recycle and
pH levels above the threshold for carbon steel corrosion.
Without saturation water recycle, corrosion control is exceedingly complex.
Although other corrosion control methods such as desalting and/or caustic injection
are often used along with wash water recirculation, these methods become even
more important if water recycle is not used. Also, alloy tubes are usually required
for the initial condensate and water reboiling region. If copper based tubes are used,
two sided pH control is needed to avoid corrosion of the copper alloy at high pH
and the carbon steel and copper components at low pH.
In general, this approach to corrosion control follows the Crude Unit Atmospheric
Overhead Corrosion Control Best Practice [8]. Although the Best Practices
approach differs from the rest of the industry, Chevron has successfully designed
and operated crude unit overheads with this philosophy since the early 1970s.

Specific Corrosives
Due to both the use of stripping steam in the atmospheric column and the presence
of water in the crude feed, large quantities of moisture are invariably present in the
atmospheric column. This moisture is, for the most part, condensed in the atmospheric column overhead-feed exchangers and overhead condensers. Where vapor
line temperatures are low (on the order of 200F), water may also condense in the
top of the atmospheric column. As a result, corrosion problems caused by liquid
water will be found throughout this area. For simplicity, the following discussion
includes the top few trays of the atmospheric column.
As mentioned, chloride salts in the crude oil form hydrochloric acid at elevated
temperatures by hydrolysis. This reaction occurs during heating of both atmospheric and vacuum column feed streams. The acid thus formed enters atmospheric
and vacuum columns and eventually leaves with the overhead product. Since HCl is
water-soluble, it is absorbed in any moisture that may condense, forming a strongly
acidic solution. While there is no evidence that HCl has any corrosive effect in the
crude distillation unit in the absence of liquid water, aqueous hydrochloric acid
solutions are the primary cause of corrosion in the overhead system, where liquid
water normally exists. Corrosion can also occur in the top part of the atmospheric
column, if liquid water exists.
Although not the primary corrosive, hydrogen sulfide also contributes to overhead
system corrosion. The usual corrosion products formed in overhead equipment are
iron and copper sulfides (on steel and copper alloys respectively). Metal sulfides
will either be stable or unstable (they will form or dissolve), depending on pH in the
system. Both iron sulfide and copper sulfide dissolve at low pH while copper sulfide
also dissolves at high pH. This is a fundamental reason why acid conditions (low
pH) corrode both copper alloys and steel, while alkaline conditions (high pH)
corrode copper alloys.

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3142 Process Controls

In the hotter areas of the crude unit, corrosion is almost exclusively controlled by
the use of suitably resistant alloys. In the crude unit overhead system, however,
process controls can minimize corrosion. Injecting water into the atmospheric
column overhead system dilutes the corrosives and stabilizes the pH. Hydrochloric
acid can be neutralized with a volatile alkaline material such as ammonia or neutralizing amine. The amount of HCl going to the overhead system can be reduced by
good desalting and the addition of caustic (sodium hydroxide) to the crude feed.
Proper process control should provide a minimum of 10 years life for carbon steel
overhead piping and have a goal of five years minimum life for carbon steel
exchanger tube bundles.

3143 Desalting
The first place in the crude unit process flow where overhead corrosion can be influenced is in the desalter. Both chemical and electrical desalting are used in Chevron
crude units. It is important that the desalter provide a consistently low salt content.
A variable salt content introduces a control problem, because changing amounts of
HCl result in pH swings in the overhead system. Monitoring of pH and controlling it
by constantly varying the rate of neutralizer injection then becomes very difficult.
Recovered oil can be an important cause of pH instability. From the corrosion engineers view point, the recovered oil should be added to the crude as far upstream as
possible to facilitate removal in the desalter. If it is fed directly to the atmospheric
column because of heat exchanger and furnace fouling concerns, recovered oil
raises the average amount and variability of chlorides going overhead. Any sources
of increased or fluctuating chloride levels increase the difficulty of controlling overhead pH and corrosion.

3144 Caustic Injection

Similar to good desalting, caustic injection is a very effective way of reducing HCl
going to the overhead. When injected into the crude between the last crude preheat
exchanger and the atmospheric furnace, caustic (sodium hydroxide) combines with
HCl as it forms. As a result, the chlorides leave the plant in the vacuum column
residuum stream, as undecomposed sodium chloride. With good desalter operation
and caustic addition to the crude, it should be possible to reduce overhead chloride
levels to 1020 ppm, as measured in the accumulator drum water.
While caustic injection helps reduce overhead corrosion, it can cause other problems if not properly applied. These problems include:

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Concentrated caustic can cause stress corrosion cracking and general corrosion
of piping and exchangers downstream of the injection point.

Caustic can damage downstream catalysts.

Caustic can cause furnace fouling. This phenomenon has not been seen in crude
furnaces, but it has occurred in coker furnaces.

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Caustic can cause unacceptable sodium carryover in the coke produced in coker
units.

Risks of stress corrosion cracking and corrosion can be mitigated by utilizing the
Caustic Injection Facilities Standard Design [2]. Where crude unit residuum is fed
to a coker or a catalytic process, such as an RDS, the risks to the catalyst must be
studied before injecting caustic in the crude unit.

3145 Wash Water Recirculation

One important element of an overhead corrosion control system is atmospheric
overhead condensed water recirculation. Carbon and low alloy steel corrosion first
occurs where heat exchange surfaces operate below the water dew point and vapors
are above the water dew point. In this region, water, HCl, and neutralizer condense
together, and then partially or completely evaporate. During evaporation, water and
neutralizer preferentially return to the vapor while chloride ions remain in the
aqueous phase resulting in a low pH. Neutralizers are ineffective in this
region. Saturation water recycle is the only way to control this problem of
condensation/evaporation.
With saturation water recycle, the water vaporization cools the overhead vapor
stream to its water dew point (or below). This avoids both the depressed pH and the
high HCl content of the dewpoint liquid. The large reservoir of recirculating water
greatly contributes to pH stability, making pH control much easier. Quenching
through the water dewpoint also prevents ammonium chloride salt deposition and
underdeposit corrosion.
Saturation water recycle involves withdrawing the condensed water from the accumulator drum, and reinjecting it into the overhead vapor line. The water should be
injected through a distribution nozzle pointing downstream. It should be located as
far upstream of the first overhead exchanger as possible to promote mixing and
vaporization. The water recirculation rate must use 3070% more water than would
be required if equilibrium were achieved, in order to achieve saturation and to
insure that a reasonable percentage of the water remains unvaporized. Similar to any
injection point, the recycle water injection area should be monitored for corrosion.
We have seen corrosion of the overhead line where inadequate mixing occurred.
Empirical methods are required to assess whether or not saturation has been
achieved and to establish operating guidelines to consistently achieve saturation. A
simple method, in concept, is to measure vapor temperature as a function of water
recycle rate. At saturation, the reduction in vapor temperature with increasing
recycle rate abruptly ceases. Measuring vapor temperature with nearby liquid at a
substantially different temperature is not simple and requires some experimentation.
The most significant disadvantage of water recirculation is loss of preheat obtained
in the overhead-feed exchangers. Chevron units built since the 1970s have been
designed to accommodate water recirculation, but earlier units may be impacted by
the loss of preheat. Another disadvantage is that wet reflux back to the column
results in tray salting and corrosion. Chevron experience, however, is that the benefits of water washing generally far outweigh the disadvantages.

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3146 Neutralization
No matter how effective desalting and caustic injection may be, some hydrogen
chloride (HCl) will always be evolved when the crude is heated. Being volatile, the
HCl will go overhead in the atmospheric and (to a lesser extent) the vacuum
columns. It will be absorbed in the condensing water, where it will form a hydrochloric acid solution. This acid is so corrosive that without process control countermeasures, corrosion prevention would require the use of expensive alloys such as
Hastelloy B or Hastelloy C. Water recirculation dilutes the acid, but neutralization is
required to raise the pH. The industry has adopted the practice of neutralizing the
acid by injecting either ammonia or a neutralizing amine into the overhead system.
The Company Best Practice is to use aqueous ammonia as the neutralizer, unless a
plants specific design and operation limit its effectiveness. If questions about the
appropriate neutralizer arise, consult with a Company Materials Engineer. The
choice should not be left to chemical suppliers, who may overemphasize the benefits of their chemicals and downplay the disadvantages.

Ammonia
Ammonia is an excellent neutralizer, is readily available, is relatively inexpensive,
and causes no downstream fouling problems. In the aqueous form it is also convenient and easily controlled. Anhydrous ammonia is not recommended because injection rates are hard to control and greatly influenced by atmospheric temperature
changes.
Anhydrous or aqueous ammonia can be purchased, but they should be diluted to a
10 wt % solution before injection into the crude unit overhead. Dilution water
should contain no more that 25 ppm of total dissolved solids in order to prevent
deposition in the overhead system. The ammonia should be injected into a sidecut
stripper vapor return line or (preferably) into the column overhead vapor line
through an injection nozzle and reliable pumping system. An accurate and reliable
measurement of ammonia flow rates is also important for maintaining system
control. Design recommendations are further detailed in the CRTC document
Design Recommendations Aqueous Ammonia System Corrosion Control Crude
Until Overhead Systems. [3]
If water injection is sufficient to achieve saturation, evaporation ceases and
ammonia neutralization becomes effective. As the vapors pass through the overhead system and are cooled, increasing amounts of condensing water remain as
liquid. HCl and neutralizer are absorbed at different rates. In an HCl/NH3 system,
the HCl is absorbed more rapidly, so the initial liquid is relatively acidic. As
condensation proceeds, more ammonia is absorbed in the liquid and the pH rises.
Corrosion continues wherever low pH water is present.
Unfortunately if water injection is insufficient, corrosive ammonium chloride
deposits can form. As condensing water has a dew point, condensing ammonium
chloride has a sublimation point. Depending on the conditions in the plant, either
ammonium chloride or water may condense first. If water condenses first, the
ammonium chloride dissolves in the water and no salt deposits form. If ammonium
chloride condenses first (sublimes), salt deposits form. When ammonium chloride

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salts deposit on colder surfaces, water vapor permeates the deposit and condenses
on the surface. The resulting aqueous ammonium chloride film is highly corrosive
and causes pitting.

Neutralizing Amines
Chemical vendors have long advocated the use of neutralizing amine rather than
ammonia for overhead pH control. They claim that using amines prevents the low
pH in the initial water condensate which is ascribed to ammonia. They fail to point
out these disadvantages, however:

Amines are much more expensive than ammonia.

Their high cost prohibits using enough to raise the pH to an optimal level.

Condensation of corrosive amine hydrochloride salts can occur at temperatures

well above the water dew point.

Neutralizing amines and their reaction products can cause fouling, corrosion,
and carry chlorides into downstream processes.

This discussion of neutralizers has focused on the atmospheric column. Similar

corrosion can also occur in the vacuum column overhead system. However, severe
corrosion seldom occurs, and it is easily remedied by addition of a small quantity of
ammonia.

3147 Target pH Range of 7.58.0

Maintaining overhead accumulator water in the 7.58.0 pH range minimizes corrosion in mixed carbon steel and copper alloy metallurgy systems. Drum pH of 7.5 to
8 produces carbon steel corrosion rates less than 10 mpy in flow environments
where vapors are water saturated. Acid water corrosion of carbon steel increases
with decreasing pH. One pH point less increases corrosion rates an order of magnitude or more in flow environments. Zero corrosion rate of carbon steel requires
saturation water recycle and drum pH greater than 8.
Conversely, copper alloy corrosion from ammonia occurs at high pH and accelerates with increasing pH. In addition, raising ammonia concentration will lower the
ammonium chloride precipitation (sublimation) temperature and lead to neutralizer
salt corrosion and plugging. Operation at the highest pH below the ammonium chloride sublimation point is the best for carbon steel. Therefore, 7.58.0 pH is the best
compromise for mixed metallurgies.
Another reason for not controlling to a pH above 8 is that pH is no longer a good
indicator of the amount of ammonia present. NH4HS buffers at about pH 8.5, so
additional NH3 just forms more NH4HS and does not produce a pH change.

3148 Corrosion Inhibitors

Theoretically, filming amine corrosion inhibitors function by forming a thin,
adsorbed film on the metal surface. This film prevents contact between the

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corrosive constituents and the metal. These high molecular weight, organic liquids
have some affinity for both oil and water. They are non-volatile, so they are not
present in the vapor phase.
Since the water phase in overhead systems causes the corrosion, a filming amine
that has a preferential affinity for water would be a likely choice for corrosion
prevention. However, these filming amines are washed away by flowing water,
especially in high velocity areas, and do not provide adequate protection. Filming
amines that have a preferential affinity for oil often do not reach the surfaces that
are water wetted, so they also fail to protect. In addition, any dead areas in the
system that are not liquid wetted will not be protected by the non-volatile filmers
when condensation and evaporation occur.
Besides their lack of effectiveness, filming amines can actually create problems.
Concentrated filmers may be corrosive. If they are not carefully diluted and
injected, they will corrode carbon steel. Inhibitors can cause fouling. They can leave
gummy deposits in instrumentation, reboilers, and heat exchangers in downstream
equipment.
A final and compelling argument against using inhibitors is that they may not be
necessary. If both overhead system design and corrosion control program are good,
corrosion rates will be low enough to make an inhibitor unnecessary. Although
chemical vendors may disagree, there is no justification for spending money on
filming amines in crude unit overheads.

3149 Materials of Construction

If process controls have not given adequate life to overhead exchanger carbon steel
tubes and if water recirculation is not feasible, more corrosion resistant and more
expensive tube materials can be used. 70-30 Cu-Ni, admiralty brass, Monel, and
titanium (ASTM B-338, Grade 2) all have better resistance to HCl corrosion than
does carbon steel. However, admiralty brass can fail by ammonia stress corrosion
cracking at a high pH and Monel is not widely used in the industry because it is very
expensive. Some titanium alloys can rapidly pit under salt deposits if tube metal
temperatures exceed 250F300F. This was also a problem when Chevron used
overhead saltwater cooled condensers. If they were water-starved, they would plug
up with waterside salt deposits. Where temperatures are high enough to cause chloride pitting of Grade 2 titanium, Grade 7 has been used with good success. One
Company refinery standardized to Grade 7 for salt water cooled condensers where
stock inlet temperatures exceeded 250F.
Corrosion in the top part of the atmospheric column is seldom so severe that an
alloy is required. As long as it is kept warm enough to stay dry and neutralizing
amine hydrochloride salts are not present, the top of the column will not corrode.
However, some older crude units with condensation in the top of the column have
shown enough metal loss after 15 to 25 years to require alloy lining. Monel or
6% Mo stainless steel is typically used, since 12% Cr steel will pit badly and the
austenitic stainless steels are subject to chloride stress corrosion cracking. Copper
alloys suffer wet H2S corrosion. 70-30 Cu-Ni valve trays failed in areas where
repeated motion at valve guides eroded off the protective sulfide scale.

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Atmospheric overhead vapor lines are constructed of carbon steel. Typically, corrosion is more moderate and alloys such as Monel are seldom justified. However,
some potential for corrosion exists here, and vapor lines should be routinely
inspected by ultrasonic and/or radiographic techniques, particularly at bends and
just downstream of bends and at injection points.

3150 Monitoring the Corrosion Control System

No corrosion control system can be effective unless it is working properly. The
following monitoring and maintenance is required.

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Monitor pH with a continuous pH analyzer. Chloride content in crude units can

be highly variable over time, so the overhead HCl concentration, neutralizer
demand, and pH will change as well. Continuous pH analysis is necessary to
observe and react to these trends. Periodic sampling can be used as a back up to
on-line continuous analysis, but it is insufficient for the tight control required
for minimizing corrosion.

Maintain and calibrate the pH analyzer on a regular basis. Since pH is

measured in the accumulator water, oil and solids will be present that are detrimental to on-line sampling and measuring devices. The Crude Unit Overhead
pH Analyzer System recommended in the Best Practice is designed to minimize the effects of these contaminants and provide reliability.[8]

In conjunction with continuous pH analysis, it is important to have board

mounted control of the ammonia injection system. With fluctuating overhead
acid concentration, frequent adjustments to the ammonia flow rate are required
to maintain the proper pH. This is much more efficiently and easily done if the
flow rates are changed in the control room.

Maintain all chemical injection pumps, flow meters, and instrumentation so that
the system is a reliable, continuous ammonia (or caustic) source.

Ultimately the best way to adjust ammonia injection and maintain the correct
pH range is with closed loop control. By configuring the pH monitor system to
control the ammonia injection, changes in control can be instantaneous and
operators can be freed from the responsibility of frequent adjustments. Obviously this approach can only be implemented when a reliable on-line analyzer
and ammonia delivery system are in place. Once this is established and the loop
has been closed, periodic checks will be necessary to ensure that the system is
working properly.

Monitor the salt content of desalted crude and the chloride content of accumulator drum water.

Continuously monitor corrosion with probes located at the inlets and outlets of
the overhead exchangers, and other areas that show signs of corrosion.

Be alert for changes in process conditions that might indicate a need for additional monitoring or a shift in the corrosion control program. For example, note

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any large change in overhead vapor line temperature or a change to a new crude
that is difficult to desalt.

Inspect overhead piping onstream and equipment during turnarounds to identify any problems or inadequacies in the corrosion control program.

3151 Vacuum Column Overhead System Corrosion

The fundamental causes of corrosion in the vacuum column overhead system are
similar to those in the atmospheric overhead, but are complicated by additional
factors. The use of a steam jet ejector to create the vacuum results in a system
containing largely steam or water, with other constituents present in smaller quantities. In addition, the existence of a vacuum introduces the possibility of air leakage
into the system.
In the absence of air leakage, corrosion tends to be less severe in the vacuum
column overhead system than in the atmospheric. While both hydrogen chloride and
hydrogen sulfide are typically present, the quantity of HCl is likely to be less than in
the atmospheric overhead. In addition, the problem of ammonium chloride deposition is seldom encountered. However, air leakage into the system creates a condition not encountered in the atmospheric overhead. Where air leakage occurs,
corrosion and scaling of both steel and copper alloys can be severe and cannot
effectively be controlled by addition of ammonia or corrosion inhibitors.
If air entry into the vacuum system is prevented, acceptable corrosion protection is
generally obtained through aqueous ammonia injection to control acidity. As in the
atmospheric overhead system, it is important to avoid excessive use of ammonia,
which could lead to corrosion and stress corrosion cracking of copper alloy
condenser tubes.
During the 1980s, Chevron had several experiences with significant corrosion
(40120 mpy) in vacuum column overheads and light gas oil sidecuts [6]. Corrosion occurs at temperatures of 350-420F, which is not hot enough for high temperature H2S corrosion, but is too high for aqueous corrosion. The corrosion appears to
be controlled by a different mechanism than traditional naphthenic acid corrosion.
Whereas naphthenic acid corrosion commonly appears as grooving and pitting, this
corrosion is smooth in appearance. Although the exact mechanism is not known, the
current thinking is that the corrosion is caused by light naphthenic acids in combination with phenols and possibly chlorides.

3160 Other System Corrosion

3161 Atmospheric Column Sidecut Stripper Corrosion
In general, atmospheric column sidecuts contain no significant corrosive constituents other than a small quantity of dissolved hydrogen sulfide, which is readily
removed in the sidecut strippers. As a result, carbon steel is almost invariably
adequate for the sidecut strippers and suffers little corrosion. In those instances

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where the columns have been corroded to their minimum allowable thickness as a
result of many years service, either carbon steel or Type 405 stainless steel linings
may be applied, depending on the level of corrosion rate encountered.
However, in the newer crude units which process sour crudes at high temperatures,
significant corrosion of carbon steel is anticipated in sidecut strippers operating over
600F. For this reason, Type 405 or 410S steel cladding and internals have been
used in the hottest sidecut strippers in our newest plants.

3162 Gasoline Rectifier Corrosion

Since a large part of the hydrogen sulfide released from the crude will ultimately
find its way into the light ends system, gasoline rectifier columns will often show
the effect of wet hydrogen sulfide corrosion. While corrosion rates are usually not
excessive, the corrosion products formed by reaction of hydrogen sulfide with steel
are voluminous and often lead to plugging difficulties. The situation has been
successfully remedied through the use of corrosion inhibitors which, due to their
detergent action, tend to prevent the accumulation of excessive sulfide scale within
the column. However, these flushed out deposits may collect in downstream
equipment.

3163 Corrosion in Piping and Valves

Corrosion problems in the furnace transfer lines and in the atmospheric and vacuum
column overhead piping have been discussed previously. In general, corrosion in
other process piping will be similar to that experienced in the equipment where the
process fluid originates. For example, if a line comes from an alloy-clad column or
vessel, it is generally necessary that the line be alloy.
In plants processing sour crudes, hydrogen sulfide corrosion is likely to occur in
carbon steel atmospheric column bottoms and sidecut lines operating above about
500F. Over 700F, the life of a steel line in these services may be little more than
one year. For this reason, consider 5% Cr steel where temperatures exceed 500F.
Similarly, naphthenic acid corrosion is usually found in atmospheric and vacuum
sidecut lines when this same type of corrosion is occurring in the column from
which the line originates. Naphthenic acid corrosion of piping can be prevented
through the use of Type 316L (> 2.5% Mo) or 317L stainless steel.
Valve bodies are generally constructed of the same material as the piping in which
they are located. The conventional 12% Cr steel valve trim is generally adequate
where valve bodies are carbon steel or 5% Cr steel. For austenitic stainless steel
valves, trim should be either a matching composition or Stellite. However, there are
a few instances, such as in atmospheric column overhead systems or desalter
effluent water, where a special valve trim such as Monel may prove desirable.

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3164 Corrosion in Pumps

Due to high turbulence, considerably more corrosion may be encountered in pumps,
particularly on the impellers, than in the associated piping systems. The general
areas of usefulness of various alloys in crude unit process pumps are tabulated
below.
Cast iron

General material for pump impellers at temperatures below 450F

Carbon steel

Pump cases and impellers where corrosion is not

a serious factor

5% chrome steel and either 12% Cases and impellers, respectively, for handling
chrome steel or CA6NM
residuum and heavier sidecuts where corrosion
is due to sulfur components
Austenitic stainless steel

Vacuum column sidecut pumps when processing

highly naphthenic crudes. Under such conditions, Type 317 steel is the preferred material.

Ni-resist

Shows a pronounced advantage in corrosion

resistance over cast iron for impellers in atmospheric and vacuum overhead systems. Incremental cost is frequently quite low. Availability
may be a problem.

3165 Desalter Corrosion

Desalter vessels are typically carbon steel. They may have a heavy corrosion allowance or be protected against corrosion by a gunite (concrete) lining.
Most of our earlier desalters were bare steel. It was found that they suffered from
rapid pitting during the first few years of operation. As a result, it became the practice to gunite-line new desalters, initially the full vessel and later only the bottom
120 degrees. With the partial gunite lining, Monel flashing was used along the edge
of the gunite to prevent undercutting.
As the years progressed and the early unlined desalters remained in service, it
became apparent that the deep pits formed during early operation were not growing
with time, and the practice of gunite-lining new desalters was abandoned. Current
practice is to construct new desalters of bare steel with a heavy (-inch) corrosion
allowance.

3170 References

Chevron Corporation

1.

Piehl, R. L. Correlation of Corrosion in a Crude Distillation Unit with the

Chemistry of the Crudes, Corrosion, Vol. 16 No. 6 (June, 1960), pp. 139141.

2.

Ellis, J. R. B., and R. A. Farnham. Design Recommendations Dilute Caustic

Injection System for Crude Units, Chevron Research and Technology

3100-31

August 1999

3100 Crude Distillation Units

Corrosion Prevention and Metallurgy Manual

Company, May 8, 1978. Consult with Chevron Research and Technology

Company for possible updated design recommendations.

August 1999

3.

Wanat, W. Design Recommendations Aqueous Ammonia System Corrosion

Control Crude Unit Overhead Systems, Chevron Research and Technology
Company, November 15, 1972. Consult with Chevron Research and
Technology Company for possible updated design recommendations.

4.

Schmidt, P. C., and J. W. Skogsberg. Crude Unit Overhead Erosion - Corrosion Richmond Crude Unit No. 4 Data Evaluation, Chevron Research and
Technology Company Report, Materials and Equipment Engineering File
No. 75.16.56.02, January 6, 1978.

5.

Piehl, R. L. Naphthenic Acid Corrosion in Crude Distillation Units, Materials Performance, Vol. 27 No. 1 (January, 1988), pp. 37-43.

6.

Ploetz, J.C., Naphthenic Acid Corrosion Guidelines, Chevron Research and

Technology Company Report, Materials and Equipment Engineering File
No. 75.16.56, September 7, 1990.

7.

Shargay, C.A., Naphthenic Acid Corrosion, Chevron Research and Technology Company Report, Materials and Equipment Engineering File
No. 16.20.55.02, May 25, 1983.

8.

Crude Unit Best Practice Atmospheric Overhead Corrosion Control, originally published on Lotus Notes, also Chevron Research and Technology
Company, Materials and Equipment Engineering File No. 75.16.56.02,
June 21, 1995.

3100-32

Chevron Corporation