Technical Bulletin

BACKGROUND

Naphthenic acid corrosion (NAC) has become a growing concern in refineries during the last ten years, as
refiners are forced to process lower quality crudes in order to remain profitable. The classic discussions of
naphthenic acid corrosion by Derungs 1 and Piehl2 concentrated on crudes from California, Venezuela,
Russia and Romania. Older descriptions of naphthenic acids and their sources, such as “Petroleum Acids
and Bases” by Lochte and Littmann did the same.3 Remedies in this early work concentrated on metallurgy
and/or dilution of naphthenic acid content. In the last ten years, the list of problem crudes has been
expanded to include crudes from the North Sea, West Africa, China and India. The purpose of this
document is to present our approach to naphthenic acid corrosion control, based on our experience. Since
an understanding of the basic phenomenon is essential to controlling it, the document begins with a brief
description of the factors that influence NAC and then moves on to the control strategy.

DESCRIPTION OF NAPHTHENIC ACID CORROSION

The term, ‘naphthenic acid,’ does not refer to a single chemical structure, but rather to a class of
compounds. In the purest sense it is a five-member aliphatic ring with an alkyl chain terminating in a
carboxylic acid group. In practice, it is a complex mixture of high boiling point carboxylic acids,4 which
become selectively enriched into the heavier cuts during the distillation process and form corrosive non-
aqueous electrolytes at higher temperatures.

The main factors that influence the onset and severity of the corrosion are: naphthenic acid content,
temperature, metallurgy, sulfur content, and velocity.

Naphthenic acid content. The most common method of indexing crudes according to naphthenic acid
content is a titration method to determine total acid number (TAN) which is a measure of the number of mg
KOH required to neutralize one gram of oil. Although there are some useful rules of thumb for threshold
TAN values where onset of corrosion is to be expected, these guidelines should not be used as absolutes.
For example, Derungs uses a threshold value of 0.5 mg KOH/gram of oil for the whole crude. Rather than
look at the whole crude, Piehl based his value of 1.5 mg KOH/gram on the specific cut in question. Since
Piehl’s rule of thumb addresses the specific problem area, we prefer it.

Temperature. The early literature indicates onset of the corrosion is about 420 F (216 C). It peaks at about
500-550 (260-288 C), and diminishes in the 700-750 F (370-400 C) range. Some recent studies have shown
that the onset might be at temperatures lower than indicated in older literature. Nevertheless, it always
occurs above the aqueous dewpoint.

Metallurgy. Carbon steel is very susceptible. Upgrade to 317 stainless steel is the ultimate metallurgical
remedy. This material has a molybdenum (Mo) content of 3-4%, compared to 2-3% for 316. Some workers
have observed the need for a minimum Mo content of 2.5%. The older literature indicates adequate
corrosion resistance by 316 ss, probably because the older castings of that material achieved the Mo
threshold of 2.5%. Table 1 gives some comparative corrosion rates of different materials.

Disclaimer of Liability: Baker Petrolite Corporation (BPC) warrants to purchaser, but no third parties or others, the specifications for the product shall fall within a generally
recognized range for typical physical properties established by BPC when the product departs BPC's point of origin and that any services shall only be performed in
accordance with applicable written work documents. BPC MAKES NO OTHER WARRANTY OR GUARANTEE OF ANY KIND, EXPRESS OR IMPLIED, INCLUDING NO IMPLIED
WARRANTY OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE, REGARDING ANY SERVICES PERFORMED OR PRODUCT SUPPLIED. BPC will give purchaser
the benefit of BPC's best judgement in making interpretations of data, but does not guarantee the accuracy or correctness of such interpretations. BPC's recommendations
contained herein are advisory only and without representations as to the results. BPC shall not be liable for any indirect, special, punitive, exemplary or consequential
damages or losses from any cause whatsoever including but not limited to its negligence.
BPTB1034 (6/99)
 Technical Bulletin
Table 1. Naphthenic Acid Corrosion Rates on Various Alloys
(Mils Per Year)

Alloy Hopkinson Piehl Gutzeit3 NACE 4

1 2

C. Steel 236 26 19.7 14 - 18

5 CR- 23.6 -- -- 14 - 16
1/2 Mo
316SS Not 0.46 0.5 <1
Detected
317SS -- 0.024 -- --

1. Corrosion 83, No. 99: TAN = 1.5, Temp = 680°F, Velocity = 85ft./sec.
2. Corrosion 87, No. 196: TAN = 3.9, Temp = 520°F.
3. Materials Performance, V16, No. 10: TAN = 9.6, Temp = 455°F.
4. NACE T-8B Report on Refining Industry Corrosion, Sept. 1963.

Sulfur. Since sulfidic corrosion is another form of high temperature attack, that occurs at temperatures
starting at about 500 F(260 C), sulfur corrosion is commonly coexistent with naphthenic acid attack. Since
sulfur corrosion is caused by H2S and its precursors, most commonly occurring forms of sulfur, with the
exception of thiophenes, are potentially corrosive.5 Some workers have observed a mitigating effect on
naphthenic acid attack by sulfur.

Velocity. The characteristic localized attack is frequently observed in locations of high velocity and shear
stress, such as elbows and downstream of thermowells. In general, the attack is more severe where the
physical state of the acids is changing, e.g. vaporizing, as in a transfer line, or condensing, as in a vacuum
tower.6 Derungs has described the appearance of the attack as “…highly characteristic, varying with
increase in stream velocity from sharp-edged, crater-like holes to sharp-edged streamlined grooves.”1

Where does naphthenic acid corrosion occur? It is observed in furnace tubes, transfer lines, tower
internals, and side-cut piping of the atmospheric and vacuum towers, as depicted in Figure 1. Enrichment of
the acids into the gas oils, especially the heavy vacuum gas oil (HVGO), makes these cuts particularly
corrosive.

Disclaimer of Liability: Baker Petrolite Corporation (BPC) warrants to purchaser, but no third parties or others, the specifications for the product shall fall within a generally
recognized range for typical physical properties established by BPC when the product departs BPC's point of origin and that any services shall only be performed in
accordance with applicable written work documents. BPC MAKES NO OTHER WARRANTY OR GUARANTEE OF ANY KIND, EXPRESS OR IMPLIED, INCLUDING NO IMPLIED
WARRANTY OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE, REGARDING ANY SERVICES PERFORMED OR PRODUCT SUPPLIED. BPC will give purchaser
the benefit of BPC's best judgement in making interpretations of data, but does not guarantee the accuracy or correctness of such interpretations. BPC's recommendations
contained herein are advisory only and without representations as to the results. BPC shall not be liable for any indirect, special, punitive, exemplary or consequential
damages or losses from any cause whatsoever including but not limited to its negligence.
BPTB1034 (6/99)
 Technical Bulletin
Atmospheric Vacuum
Column Column
Desalter LVGO

Crude 450°F

Charge Diesel

AGO HVGO

550°F

600°F
275°F 500°F 650°F

Hot Crude Atmospheric 620°F 650°F

Preheat Heater
680°F
Exchangers VTB

Figure 1. Shaded area depicts the primary region of concern for naphthenic acid corrosion.

CONTROLLING NAPHTHENIC ACID CORROSION

Short of a complete metallurgical upgrade or diluting the naphthenic acids to a safe level through blending,
we have developed a successful corrosion control strategy consisting of the following tools:
♦ Crude oil and distillate analysis for naphthenic acid content
♦ Use of COOL (Crude Oil Online Library)
♦ Three different laboratory tests to study corrosion directly
♦ Field monitoring with a variety of tools
♦ Application of chemical inhibitors.

Crude oil and distillate analysis for naphthenic acid content. The presence of some naphthenic acid is an
obvious requirement for corrosion. Whereas the TAN rules of thumb for the onset of corrosion are not very
reliable, TAN and weight percent naphthenic acid at least provide warnings of potential trouble. Until
recently, TAN was used almost exclusively for this purpose, but TAN suffers from being a non-specific
measure of any source of acidity, rather than being specific to the class of compounds that are included
above in the discussion of the nature of naphthenic acids. Because TAN is very easy to determine, it is
useful for monitoring a system for changes. Determining weight percent naphthenic acid by FTIR is a more
difficult analysis to run than TAN, but it specifically measures the number of carboxylic acid groups present
in the oil. Once it has been correlated to TAN for a particular crude, its difficulty precludes it use as an
ongoing monitor. Figure 2 is a plot of TAN vs. weight percent naphthenic acid for several crudes. Because
of the wide variation in equivalent weights of the naphthenic acids from crude to crude and because TAN
looks at all acid species that are measured in the titration, the poor correlation between the two
determinations is not surprising. Since some customers are interested in weight percent naphthenic acid, it
 Technical Bulletin
is part of the total offer. Nevertheless, TAN is a much more practical day to day monitor of changes in
acidity.

Figure 2. TAN vs. Wt. % Naphthenic Acid

6

4
TAN

0
0 0.5 1 1.5 2
Wt. % Naphthenic Acid

Database. The Crude Oil On Line Database has assay and experiential data on over 400 crude oils and is in
process of being updated.

Laboratory Tests. We have several laboratory tests to help us troubleshoot the corrosivity of particular cuts.
These tests are described in detail elsewhere.7,8

MONITORING

Although these laboratory tests have been used primarily to develop chemical inhibitors and to gain some
insight into the different factors that affect naphthenic acid corrosion, we have also used them to
troubleshoot field applications. A good monitoring program is an absolutely essential requirement for
processing high naphthenic acid-containing feeds. No one monitoring tool is adequate, but rather a
combination of high temperature electrical resistance (ER) probes, ultrasonic thickness (UT) measurements,
radiography, and metal counts is required. Monitoring the acidity of corrosive cuts by means of weight
percent naphthenic acid (at least once) and TAN (monitor for changes) is also needed.

For ER probes we recommend the high temperature (HT) probes from Rohrback or the Excel probes from
Cortest. As with any probe, placement is critical. Points of high shear stress should be chosen, where
feasible.

UT measurements are usually carried out in cooperation with the refinery’s inspection department. It is
important to work with inspection to identify the locations of highest surface shear stress and monitor at
these points.

Periodic radiography scans should be performed, where possible. Although they are fairly expensive, they
have been useful in identifying areas of corrosion before the problem became critical.
 Technical Bulletin
Metal counts also sometimes provide useful information, although their interpretation is usually difficult.
Since ppm levels of Fe, Ni, and V are found in virtually all crudes, the ratio of Fe to Ni or V can be used as
an indicator of corrosion. If a significant increase in that ratio is observed in a cut, corrosion has occurred
somewhere upstream of the sample point. The problem with this monitoring tool is that it indicates only
that corrosion is taking place, but does not pinpoint the location. Furthermore, interpreting the amount of
increase in the Fe/Ni or Fe/V ratio is very difficult. A very low corrosion rate over a very wide surface area
could put a lot of Fe into the oil and produce a high Fe/Ni ratio. On the other hand, a very high corrosion
rate in a very localized area would put relatively little Fe into solution, and result in little increase in the
ratios over what they were in the crude. Since localized corrosion is usually expected with naphthenic acid,
a small increase in the ratio could produce a false sense of security.

CHEMICAL PROGRAMS

BPC has two inhibitor programs to combat naphthenic acid corrosion. Both of these programs have been
used to protect furnace tubes, transfer lines, tower internals and side-cut piping of atmospheric and vacuum
towers that were processing high naphthenic acid crudes. %. The mechanism of inhibition is the same for
both additives, i.e. formation of a very hard, adherent complex of iron and phosphorus on the metal surface.
Some refiners have expressed concern about the potential negative impact of phosphorus on downstream
catalyst, but in practice we have never encountered a problem with catalyst poisoning in any of our
applications (or even in any of our competitors applications).

BPR 81441. Patented product. Contains about 2.5% phosphorus

BPR 81425. Contains about 5-6% phosphorus.

The strategy for using these chemical inhibitors is the same. Use a very high dosage for the first few hours
to establish the protective iron/phosphorus complex. Then cut back to the maintenance dosage required to
maintain the coating. To establish the initial coating usually requires 1000 ppm for about 4 hours. If it is
impossible to deliver this much chemical in a short time, a proportionately lower dose for a proportionally
longer time period has also been used effectively.

For more specific practical details on applying these chemical programs consult the Best Practices document
on this subject.

REFERENCES

1. Derungs, W.A., “Naphthenic Acid Corrosion-An Old Enemy of the Petroleum Industry,” Corrosion,
12 (1956): p. 41.

2. Piehl, R.A., “Naphthenic Acid Corrosion in Crude Distillation Units,” CORROSION/87, paper
No. 196, (Houston, TX;NACE International, 1987).

3. Lochte, H.L. and Littmann, E.R., “Petroleum Acids and Bases,” Chemical Publishing Co., New York,
(1955).

4. Fan, T.P., “Characterization of Naphthenic Acids in Petroleum by Fast Atom Bombardment Mass
Spectrometry,” Shell Development Company, Bellaire Research Center, Houston, 1991 pp. 371-375.
 Technical Bulletin
5. American Petroleum Institute, “High Temperature Crude Oil Corrosivity Studies” API Publication
943, September 1974

6. Blanco, E.F. and Hopkinson, B., “Experience with Naphthenic Acid Corrosion In Refinery
Distillation Process Units, CORROSION/83, paper No. 99, (Houston, TX; NACE International,
1983).

7. . Zetlmeisl, M.J.“A Laboratory and Field Investigation of Naphthenic Acid Corrosion Inhibition,”
CORROSION/95, paper no. 334, (Houston, TX:NACE International, 1995)

8. Zetlmeisl, M.J., Harrell, J.B., and Campbell, J., “Controlling Naphthenic Acid Corrosion,” to be
published in Hydrocarbon Engineering, July 2000.

Disclaimer of Liability: Baker Petrolite Corporation (BPC) warrants to purchaser, but no third parties or others, the specifications for the product shall fall within a generally
recognized range for typical physical properties established by BPC when the product departs BPC's point of origin and that any services shall only be performed in
accordance with applicable written work documents. BPC MAKES NO OTHER WARRANTY OR GUARANTEE OF ANY KIND, EXPRESS OR IMPLIED, INCLUDING NO IMPLIED
WARRANTY OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE, REGARDING ANY SERVICES PERFORMED OR PRODUCT SUPPLIED. BPC will give purchaser
the benefit of BPC's best judgement in making interpretations of data, but does not guarantee the accuracy or correctness of such interpretations. BPC's recommendations
contained herein are advisory only and without representations as to the results. BPC shall not be liable for any indirect, special, punitive, exemplary or consequential
damages or losses from any cause whatsoever including but not limited to its negligence.
BPTB1034 (6/99)