Establishing the Reasons and Type of the Enhanced Corrosion in
the Crude Oil Atmospheric Distillation Unit
Nedialka Petkova*, Mariyana Angelova, Petko Petkov
University Prof. Asen Zlatarov, Department of Industrial management,
8010 Bourgas, Bulgaria
E-mail: nelco@[Link]; angelova_m@[Link]; rector@[Link].
Key Word: Naphthenic acids, high temperature corrosion, corrosion in an Atmospheric
Distillation Unit.
The aim of the present paper is to establish the reasons for the enhanced
corrosion observed in the crude oil atmospheric distillation unit of LUKoil
Neftochim Bourgas Co. The results from the investigation define the measures
necessary to be taken to reduce the risk of accidents and prove the necessity for
preliminary monitoring of the sulfur and naphthenic acids content in the raw
material processed. World experience shows that the processing of petroleum
with high content of naphthenic acids results in accelerated degradation of
equipment in the temperature range 200 - 400C. Under these conditions
characteristic for the middle-distillate fractions of the atmospheric and vacuum
installations, naphthenic acids of low molecular weight are produced which are
highly active towards metals. To avoid unwanted consequences for the
technological equipment, it is necessary to determine the total acidity number
(TAN) and naphthenic acids number (NAN), beside the routine analyses. When the
presence of naphthenic acids exceeds certain limits then proper combination of
measures should be taken to protect the petroleum processing installation against
corrosion.
INTRODUCTION
Naphthenic acids are classified as carboxylic mono-acids with general formula
R(CH2)nCOOH, where R is some cycloaliphatic structure. A number of authors use the
term naphthenic acids as reference to all the carboxylic acids present in petroleum.
The heavy kinds of petroleum, due to their specific origin, usually have higher content
of acids while paraffin petroleum contains smaller number of acids 1,5. In his paper,
Trond Erik Havre characterized the naphthenic acids as the products of biodegradation
of hydrocarbons in petroleum. They are biological markers closely related to ripening
1,2
and the degree of biological degradation in the petroleum fields .
Marit-Helen Ese and Peter K. Kilpatrick* considered naphthenic acids to be
complex mixture of compounds containing 10 to 50 carbon atoms and 1 to 6 saturated
rings bonded by short alkyl chain ending with carboxylic group. The distribution of
carbon content and number of rings differs among the different kinds of petroleum and
the distillate fractions. Naphthenic acids of small TAN and medium molecular weight
have quite different structures1,3. Figure 1 shows examples of structures of naphthenic
acids which might be found in crude oils.
1
Fig. 1 Examples of structures of naphthenic acids that may be found in crude oils.
n his presentation Naphthenic Acid. Corrosion Control Strategies, Randy
Rechtien visualized the action mechanism of naphthenic acids based on their
6
physicochemical properties . Generally, naphthenic acids are soluble in hydrocarbon
media and only the low molecular weight ones are soluble in water. They are
concentrated in the temperature interval of kerosene and diesel fractions and affect
primarily the zones of high fluid velocity5,11. They react with iron to form iron
naphthenate and release atomic hydrogen which diffuses through the metal and
remains as molecular hydrogen on its surface 6:
0
1) Fe + 2RCOOH Fe(RCOO)2 + H
0
2) 2 H H2
Naphthenic corrosion is an aggressive form of local corrosion related to the
processing of crude oil with total acidity number higher than 0.5 mgKOH/gm. he
typical naphthenic corrosion is observed in the temperature interval 200 400C.
According to the expert opinion of [Link] in the Nalco report, corrosion rate
increases thrice per each 55C increase of temperature in this interval4. Vrijhoeven
suggested that the attack is usually limited within the zones where the condensing
acids could contact with metal surface (e.g. lower part of the plates), i.e. where the
4
protective layer of hydrocarbons diluting the acids is missing .
APPROACH AND EXPERIMENTAL PROCEDURE
The aim of the present study is to establish the reasons for a real accident
observed in the installation for atmospheric distillation of petroleum of LUKoil Neftochim
Bourgas Co. and taking precaution measures to prevent such accidents in future.
By the end of March 2007, during planned maintenance of the installation for
atmospheric distillation 4, some plates of the rectification column (between 6th and 12th)
were found sunk. The rectification column is manufactured from bimetal with basic
material low alloyed steel 16GS and the cladding steel 0X13. Metal identification
analyses carried out showed that the binding elements plates, bolts, nuts, etc. have
been made of steels 1X13, 2X13 and X18N9T while the main beams were made of
carbon steel St3. According to literary data, steels 0X13, 1X13 and 2X13 are stable in
2
media of average aggressiveness containing small amounts of hydrochloric acid and
hydrogen sulfide at temperatures up to 500C. Steel X18N9T is reported to be stable in
oxidative, acidic and alkali media9.
After thorough examination of the corroded equipment, the metal surface of the
main beams was found to be highly corroded with deep pits, at some places even
9
perforated . The type of corrosion pattern is quite specific, resembling lace. Relating
the type of corrosion with the temperature interval where it had occurred and taking into
4,5
account some literary reports , it could be suggested that it had been caused by the
presence of naphthenic acids. The results obtained from the visual examination were
confirmed by the microscope analysis carried out by Nalco Co.
The metal sample shown in Fig.2 is part of a beam mounted at the inlet of the
rectification column, subjected to temperatures up to 360C. The sample surface is
covered with spots and pits of oval shape, with perforations at some places. The
average beam thickness was measured to be 4.6 mm, compared to the initial thickness
4
of 6.0 mm. All surfaces were covered with fine black sulfide layer .
Fig. 2 A part of plate on the tray section Fig. 3 Binding elements plates,
bolts and nuts on the tray section
Figure 3 shows the binding elements to the same beam, made of high alloyed
kinds of steel. The photograph clearly shows that the corrosion affected only the
9
beam .
The microscope analyses of part of the beam (Fig.4) showed that the metal
microstructure contained metal carbides and manganese sulfide precipitated in the
ferrite mixture 4.
Fig. 4 Metal microstructure consisting of iron Fig. 5 Rounded depression profile that
carbides and elongated manganese sulfide is lined by a thin corrosion product
precipitates in a matrix of ferrite layer
3
4
Metal surface covered with fine layer of iron corrosion products, mainly FeS , is
presented in Fig. 5.
It is well known that iron sulfide exerts certain protective effect against
15,16
naphthenic acids. In this respect, some researchers stated that petroleum with high
TAN values and sulfur content u to 2-3% has lower corrosion activity compared to
petroleum with lower TAN values and lower sulfur content. The reason for this is the
lack of sulfur necessary for the formation of protective FeS layer so the naphthenic
acids attack directly the unprotected metal surface.
RESULTS AND DISCUSSION
Despite the undisputable proofs for the presence of naphthenic corrosion, a
comparison of the petroleum properties for this period was carried out to exclude the
probability for effects of other corrosion-active components (Table 1)*.
In the period investigated, there were no significant divergences in the
properties of the Russian export mixture for the individual tanker samples. Generally, it
can be concluded that the values comply with the certified ones.
Table 1 Average surveyor properties of petroleum from October 2006 to April 2007.
Date
Crude data Test method
10.06 11.06 12.06 01.07 02.07 03.07 04.07
1. Density at 20, 0,867 0,863 0,865 0,867 0,866 0,864 0,864
g /m EN ISO 3675 0 9 3 7 1 9 4
I 31,07 31,65 31,39 30,94 31,24 31,46 31,55
2. Sulfur, % STM- 443 1,39 1,31 1,16 1,30 1,40 1,31 1,22
3. Water, % STM-D 4006 0,020 trace trace trace 0,15 0,15 0,25
4. Salt, mg/l BDS 5502 6 6 12 5 11 13 10
0,006 0,006 0,008 0,006 0,005 0,006 0,006
ST SIV 2876
5. Sediments, % 2 1 6 9 4 6 2
Table 1* The average surveyor testing of petroleum were performed by the independent arbitrary
laboratory Saybolt
Table 2 General properties of Russian export mixture (REBCO) certified according to
GOST TU 39-1623-93:
Density at Water and
Sulfur, Salt,
30 sediments,
% mg/l
g /m API m %
0,870 32 1,8 100 1,2
The next step in the investigation was the check the content of chlorides at the inlet of
the atmospheric distillation installation, after desalination and by the processes of
rectification.
4
Chart 1 Content of chlorides at the inlet of atmospheric distillation 4 and after the
electric dehydrators for the period October 2006 April 2007
50.00
45.00
40.00
35.00
NaCl, mg/l
30.00
Crude oil
25.00
Desalted Crude oil
20.00
15.00
10.00
5.00
0.00
00
6 06 06 06 06 06 06 07 00
7 07 00
7 07 00
7 07
00
7
/2 20 20 20 20 20 20 20 /2 20 /2 20 /2 20 /2
/3 7/ 1/ 4/ 8/ 2/ 6/ 9/ 23 6/ 20 6/ 20
3/
17
10 /1 /3 /1 /2 /1 /2 1/ 1/ 2/ 2/ 3/ 3/ 4/ 4/
10 10 11 11 12 12
Date
Chart 2 Content of chlorides in separation waters after benzene removing and
rectification columns for the period October 2006 April 2007
35.00
30.00
25.00
NaCl, mg/l
20.00
Content of chloride ih the separation w ater on -101
Content of chloride in the separation w ater on -102
15.00
10.00
5.00
0.00
00
6 06 06 06 06 06 06 07 00
7 07 00
7 07 00
7 07 00
7
/2 20 20 20 20 20 20 20 /2 20 /2 20 /2 20 /2
/3 7/ 1/ 4/ 8/ 2/ 6/ 9/ 23 6/ 20 6/ 20 3/ 17
10 /1 /3 /1 /2 /1 /2 1/ 1/ 2/ 2/ 3/ 3/ 4/ 4/
10 10 11 11 12 12
Date
As can be seen from Charts 1 and 2, there were some individual high values of
chlorides content, e.g. after the electric dehydrators and after the columns which are
probably due to erroneous sample taking or ineffective performance of the electric
dehydrators. The increased chlorides content after the rectification column, compared
to the initial petroleum composition, clearly indicated for the presence of organically
bonded chlorides in petroleum and their probable decomposition in the oven. According
to H. Shalaby, the organic chlorides are not removed after desalination and they tend to
decompose under high temperature to form HCl which, in turn, reduces the pH values
and initiate accelerated corrosion in the up most sections of the distillation installation
and the condenser unit 12. It should be noted here that this kind of corrosion is totally
different from the one induced by the high content of naphthenic acids.
The laboratory testing of the separation waters after benzene removing and
rectification columns in the period October 2006 April 2007 did not show deviations in
pH values and presence of soluble iron. This is due to the efficient performance of the
inhibitor system implemented for protection of the equipment in these units. This aim of
this protection is to block out the corrosion processes initiated by the presence of salts
and sulfur containing components in the flow. It consists of neutralizing and film-forming
inhibitors17,18. Unfortunately, these types of inhibitors do not have protecting effect
against the naphthenic acids.
Since only petroleum of Russian origin has been processed for the recent years,
the total acidity number (TAN) has not been measured for this period. After the
accident, the TAN of the petroleum supplied and the distillate fractions obtained were
13 14
determined according to ASTM D 664 - 95 and ASTM D 3242 -01 .
5
Table 3 Total acidity number of an average petroleum sample and distillate fractions in
March (analyses of the Research Laboratory of LUKoil Neftochim Bourgas Co):
TAN,
Middle test - March Test method
mgKOH/g
Crude oil 0,56 ASTM D 664 - 95
TBP cut point: C5 - 110 0,018
110 - 180 0,067
ASTM D 3242 -01
180 - 240 0,179
240 - 360 0,287
The values of TAN for petroleum supplied in March 2007 were above the limit of
11,15
0,5 mgKOH/g , - a value above which the petroleum is considered to be acidic and
special measures should be taken before its processing.
In the course of the events during this period, at the beginning of April 2007 the
performance of the atmospheric distillation installation 4 had to interrupted emergently
due to a problem with the oven before the rectification column. Immediate examination
showed that the serpentine in third convection section was punctured. The reason for
this was found to be changed material the serpentine was made from carbon steel
St20 instead of the thermally resistant steel 15X5M. Ultrasonic measurements showed
that the serpentine wall thickness observed (1,6 2,2 mm)10 was much smaller then the
7,8
designed one (8 mm). As it has been reported for similar ovens and technological
conditions petroleum temperature at the inlet 240C, temperature at radiant chamber
outlet about 860C, temperature at the convection chamber outlet about 350-400C
the use of carbon steels St10 and St20 is allowed only for the tubing in the convection
part, i.e. where the temperature is below 400C.
Back in 1874 Suhotin et al. published their thorough investigation on this
problem. The choice of the construction materials for the processing of petroleum with
high sulfur content and naphthenic acids is crucial, as can be seen from the data
5
presented in Table 4 .
The steel samples were tested at sulfur content in petroleum 1.2% and total
acidity number 0.4 0.5 mgKOH/mg, i.e. properties similar to those of the export
mixture of Russian origin processed. According to Suhotin et al., the depth of corrosion
penetration in St.3 for 42 days in the rectification column was 6.1 mm/y which
undoubtedly indicated for accelerated corrosion of carbon and low alloyed steel grades
under increased content of naphthenic acids and the technological conditions
5
employed . The damage observed in the LUKoil Neftochim Bourgas Co., mainly on the
beams supporting the plates in the zone of petroleum inflow into the column were
caused for about the same period of time which also sustains the opinion that severe
naphthenic corrosion had taken place.
6
Table 4 Corrosion rate of different grades of steel under service testing of an
installation for atmospheric distillation of petroleum:
Petroleum
Corrosion
Sample exposition Steel grade Acidity, Sulfur
rate, mm/y
mgKOH/ml content, %
1. Oven tubes Carbon steel
Petroleum transfer Carbon steel
5,75
2. line of atmospheric
column
St3 320-380 1,2
6,1
Rectification column X5 2,6
3. (tests duration 1000 0X13 0,86
h) X18N10 0,017
CONCLUSION
In conclusion, we can summarize the well known practical measures of utmost
importance which should be taken to protect the technological equipment from
naphthenic corrosion used in refineries processing crude oil with high content of
naphthenic acids: proper management of the petroleum supplies, definition of the
critical factors and assessment of the risk in its processing, reasonable blending of the
different batches, choice of suitable material for the equipment, chemical inhibition,
continuous monitoring and automated corrosion control, optimization of the corrosion
management programs.
The critical factors of crude oil which must be controlled are these indicating its
corrosion aggressiveness: density, content of water soluble salts, total sulfur content,
organically bonded chlorine, total acidity number (TAN), naphthenic acids content
(NAN), contents of metals Ni, V, Fe, Hg, Se, etc. The corrosion effect of the
naphthenic acids can be diminished by blending petroleum of high neutralization
number with one of lower neutralization number to obtain raw material with acidity
number not higher than 0,5 mgKOH/g. The choice of suitable construction material
means the use of corrosion-resistant steel like austenite stainless steel grades
chromium-nickel-molybdenum alloyed ones which have excellent resistance to raw
materials containing hydrogen sulfide, chlorides, organic and inorganic acids under
high temperature. The report of Nalco Co. stated that steels of grade 316SS or 317SS
with molybdenum content above 3% are the most suitable for manufacturing of the
technological equipment working under these conditions. The introduction of automated
corrosion monitoring would also allow the optimization of the amount of inhibitors
introduced to change the medium characteristics or technological parameters. The
methods of corrosion control in the presence of naphthenic acids are simply
determination of metal loss using corrosion coupons, ultrasonic or hydrogen infiltration
measurement of the thicknesses of equipment walls.
Obviously, when supplying petroleum with high content of naphthenic acids, it is
necessary to take all precaution measures before letting it into the installation. The
processing method should be carefully selected to avoid hazardous situations and rapid
deterioration of the technological equipment at certain points of the installation for
atmospheric distillation of petroleum.
7
REFERENCES
Rechtienr Petrolite Corporation
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