1. No category

152
UDС 620.195
RESEARCH OF THE INFLUENCE OF SAMPLE WITNESS
CHARACTERISTICS ON THE EFFICIENCY OF CORROSION
MONITORING
ИССЛЕДОВАНИЕ ВЛИЯНИЯ ХАРАКТЕРИСТИК ОБРАЗЦОВСВИДЕТЕЛЕЙ НА ЭФФЕКТИВНОСТЬ КОРРОЗИОННОГО
МОНИТОРИНГА
A.P. Efremenko, A.Y. Spasсhenko, I.F. Sadretdinov, K.V. Aleksandrova,
FSBEI НРЕ “Ufa State Petroleum Technological University”,
Ufa, the Russian Federation
LLС “R&D Center Salavatnefteorgsyntez”, Salavat, the Russian Federation
Ефременко А.П., Спащенко А.Ю., Садретдинов И.Ф., Александрова К.В.,
ФГБОУ ВПО «Уфимский государственный нефтяной технический
университет», г. Уфа, Российская Федерация
ООО «Научно-технический центр Салаватнефтеоргсинтез»,
г. Салават, Российская Федерация
email: [email protected]
Abstract. In this paper the advantages of corrosion monitoring are described
using gravimetric witnesses samples for oil production and refining companies,
the necessity and effectiveness of their use are founded, the additional
capabilities of the method are shown, especially control of deposits on the
internal surfaces of equipment and their effect on the corrosion rate. The paper
presents data on the coupons geometric form, it is noted that witnesses samples
of rectangular shape are the most widespread.
This article also presents information about the modernization of coupon
holders for existing CDU VDU - 4 of JSC "Gazprom neftekhim Salavat", the
advantages of suggested design are described, data of corrosion monitoring on
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153
the unit since December, 2013 are provided. Noted, that to hold a valid
comparison of different coupons characteristics in an industrial environment is
not possible, due to the lack of coupon holders substitutability on different
corrosion control sites of unit. In this regard, comparative tests of coupons were
conducted in the laboratory, coupons selected for the tests were rectangular,
disk-shaped and rectangular with a weld, and the basis for coupon selection is
shown. Lab installation was prepared for tests which scheme is given. All
samples were made from the same material - BSt3sp by GOST 380 – 2005.
Tests were carried out in 50% of mass water solution of lemon acid, duration of
each series of tests were 3, 6 and 9 hours. By the tests results the mass loss of
samples was defined and mass and deep indicator of corrosion rate was
calculated. On the basis of obtained data, diagrams of corrosion rates
dependence on the sample witness type and tests time were made. The received
results showed that coupons with an additional source of residual internal
stresses in the form of weld are exposed to more serious corrosive attack (show
greater tendency to corrosion) in comparison with rectangular and disk-shaped
coupons. The explanation of revealed regularity is given in the article using data
on macro and micro electrochemical heterogeneity of welded connections and
the doctrine about electrochemical potentials. Thus, using samples witnesses
that have additional source of internal stresses such a weld, for corrosion
monitoring make it as close as possible to the actual conditions.
Аннотация.
В
работе
описаны
преимущества
коррозионного
мониторинга с использованием гравиметрических образцов-свидетелей на
предприятиях
необходимость
нефтедобычи
и
и
эффективность
нефтепереработки,
их
обоснована
применения,
показаны
дополнительные возможности метода, в частности контроль отложений на
внутренних поверхностях оборудования и их влияния на скорость
коррозии. Приведены данные по геометрической форме купонов,
отмечено, что наибольшее распространение получили образцы-свидетели
прямоугольной формы.
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154
В статье также представлены сведения о проведенной модернизации
купонодержателей для действующей установки ЭЛОУ-АВТ-4 ОАО
«Газпром нефтехим Салават», описаны достоинства предложенной
конструкции, приведены данные коррозионного мониторинга установки с
декабря 2013 г. Отмечено, что провести корректное сравнение купонов
различных характеристик в промышленных условиях не представляется
возможным, ввиду отсутствия взаимозаменяемости купонодержателей для
различных узлов контроля коррозии установки. В связи с этим были
проведены сравнительные испытания купонов в лабораторных условиях,
для этого выбраны купоны прямоугольной и дискообразной формы,
а также купон прямоугольной формы со сварным швом, приведено
обоснование выбора данных купонов. Для испытаний была подготовлена
лабораторная установка, представлена схема установки. Все образцы были
изготовлены из одинакового материала – ВСт3сп ГОСТ 380 – 2005.
Испытания проводились в 50% масс. водном растворе лимонной кислоты,
продолжительность каждой серии испытаний составила 3, 6 и 9 часов. По
результатам испытаний была определена потеря массы образцов и
рассчитаны массовый и глубинный показатель скорости коррозии. На
основе полученных данных были построены графики зависимости
скоростей коррозии от типа образца-свидетеля и от времени испытаний.
Полученные результаты показали, что купоны прямоугольной формы с
дополнительным источником остаточных внутренних напряжений в виде
сварного шва, в сравнении с прямоугольным и дискообразным купонами,
подвергаются
более
значительному
коррозионному
воздействию
(проявляют большую склонность к коррозии). В статье приведено
объяснение выявленной закономерности с привлечением данных о макрои микроэлектрохимической неоднородности сварных соединений и учения
об электрохимических потенциалах. Таким образом, наличие у образцовсвидетелей остаточных внутренних напряжений в виде сварного шва
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155
делает коррозионный мониторинг с его использованием максимально
приближенным к реальным условиям.
Key words: corrosion monitoring, witness sample, corrosion coupon,
corrosion inhibitor, corrosion rate, galvanic couple, internal stress.
Ключевые слова: коррозионный мониторинг, образец-свидетель,
купон коррозии, ингибитор коррозии, скорость коррозии, гальваническая
пара, внутреннее напряжение.
In order to detect and prevent the destruction of corrosion hazardous areas of
refineries equipment, as well as for the selection and effective use of corrosion
inhibitors it is necessary to conduct corrosion monitoring.
The most widely used and quite effective method of corrosion monitoring is
the application of gravimetric corrosion witness samples (corrosion coupons)
[1].
Witness samples can be both a source of information about the condition of
the equipment at the moment, and a base for implementation of measures to
prevent accidents. With their help, possible both a quantitative measurement of
the corrosion rate, and the visual determination of the corrosion type. Also,
corrosion coupons may be used to determine the probable replacement of
existing equipment material by one that is more resistant to these conditions [2].
Now coupons of different types and forms are available. Their number
includes samples of rectangular and disk-shaped form, in the form of half rings,
the rings which surface has a certain roughness, and samples with additional
residual internal stress.
Rectangular samples are the most widely used. They have the largest surface
area among all given above at identical conditions of assembling, do not require
sophisticated equipment for installation in the pipeline, and have no noticeable
effect on the hydrodynamics of the flow [3].
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156
Another advantage of the corrosion witness samples is their ability to detect
the presence of corrosion deposits on the equipment walls. Corrosion inhibitors
typically work by forming a protective film on the surface of the equipment. In
the presence of depositions inhibitor’s film cannot fully cover the metal surface
and the protective effect of inhibiting decreases, consequently, under the layer of
depositions corrosion continues, which usually has ulcerative nature. Since
corrosion coupons may be exhibited for a long time on their surface deposits
similar to deposits on the walls of equipment are accumulated, whereby it is
possible to study the influence of deposits on the corrosion rate [4,5].
On CDU VDU - 4 of JSC "Gazprom neftekhim Salavat" was decided to
upgrade the witness samples holders, in such a way that three discoid coupon
were installed on each coupon holder. It is important that the coupons were
isolated from the stem and adjacent witness samples by the teflon bushings
(Figure 1).
The advantages of this design are the simplicity, reliability, ability to install
additional coupons only by changing the width of teflon bushings without
changing the design of coupon holder.
Figure 1. Witness samples holders for CDU VDU – 4
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157
One more advantage of disk-shaped coupons is when exhibiting rectangular
samples it is impossible to tell with an accuracy, under what corner to movement
of a stream samples are and what is the way of their flow over by stream. In case
of disk-shaped coupons, the smooth flow over of samples with a stream is
provided, thanks to their form.
If we compare the surface area of the samples, that, when mounting through
the same nozzle, rectangular coupons may be produced with greater surface area
than the disk-shaped. The question arises how the surface area and shape of
coupons affects on the efficiency and accuracy of corrosion monitoring results.
Due to small pipeline diameter of the one of witness samples installation
sites (1PA) of the CDU VDU – 4 retained rectangular samples. Table 1 shows
the corrosion monitoring CDU VDU – 4 with witness samples.
First pumparound
Average corrosion
rate, mm/year
Brand of
coupons
steel.
Corrosion
pattern
(visual
inspection)
Average weight loss,
g.
Brand of
coupons
steel.
Corrosion
pattern
(visual
inspection)
Average corrosion
rate, mm/year
Average weight loss,
g.
Average corrosion
rate, mm/year
End of exposure
Date
Beginning of exposure
Gasoline from the K-210
Witness samples fitting position
Gasoline from the K-220
Average weight loss,
g.
Table 1. Results of corrosion monitoring CDU VDU – 4
Brand of
coupons steel.
Corrosion
pattern (visual
inspection)
After upgrading of coupon holders conducted Ltd. “R&D center Salavatnefteorgsyntez”
7.11. 9.12.
St.20,
St.20,
Obstipation at the coupons
0.0139 0.009
0.0061 0.004
2013 2013
uniform
uniform
installation site
St.3,
ulcerative, a
9.12. 10.01.
St.3,
St.3,
large amount
0.0788 0.054
0.0174 0.012
0.2425
0.259
2013 2013
ulcerative
uniform
of black
deposits on the
coupons
St.3, uniform
10.01. 11.02.
St.3,
St.3,
0.0250 0.016
0.0256 0.017
0.0620
0.064 black deposits
2014 2014
uniform
uniform
on the coupons
11.02. 12.03.
St.3,
St.3,
0.0256 0.018
0.0237 0.017
0.0196
0.022 St.3, uniform
2014 2014
uniform
uniform
The obtained data do not allow fully evaluating the applicability and
effectiveness of using rectangular and disc-shaped witness samples, because
coupon holders for various corrosion control installation sites are not
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158
interchangeable, so it was decided to conduct a comparative analysis of various
samples of witnesses in a laboratory experiment to ensure the same test
conditions.
As objects of research chose the witness samples differing in shape, surface
area and the presence of residual internal stresses (Figure 2). Selection of the
submitted coupon samples caused by the following: rectangular witness sample
(sample R) is the most common, easy to manufacture; discoid coupon (sample
D) when mounted in a pipeline provides minimal flow resistance thanks to
constant positioning from all angles during exposure; coupon with additional
source of internal stresses such a weld (sample RS) is selected for the reason that
the main way of pipelines and equipment connection is welded connection
which change structure of the main metal in the heat affected zone, reducing
resistance to corrosion therefore existence of a welded seam does these samples
the most approximate to real conditions. All samples were made from the same
material - BSt3sp by GOST 380 – 2005. Tests were carried out in 50% of mass
water solution of lemon acid.
Figure 2. Corrosion witness samples
a – witness sample rectangular (R); b – witness sample disk-shaped (D);
c – witness sample rectangular shape with residual internal stress (RS).
The measurement results and the surface area of the samples are presented in
Table 2.
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159
Table 2. Parameters of witness samples
Sample №
Sample shape
D1
D2
D3
R1
R2
R3
RS1
RS2
RS3
disk
disk
disk
rectangle
rectangle
rectangle
rectangle
rectangle
rectangle
The surface area of the
sample, m2
0.0019987
0.0019991
0.0019941
0.0037421
0.0036883
0.0036804
0.0036255
0.003655
0.0036546
Sample weight before the
test, g
22.6829
22.7474
22.452
44.3604
44.3134
43.4432
41.9859
42.6725
41.8801
For the tests, lab installation presented in Figure 3 was prepared.
Figure 3. Laboratory installation
1 – circulation pump; 2 – feed vessel; 3 – cylinder; 4 – witness sample
Feed vessel 2 was filled with corrosive media - 50% of mass water solution
of lemon acid, circulation pump 1 pumps corrosive media from the feed vessel 2
through the cylinder 3, where the witness samples 4 were installed. Depending
on the frequency of the pump motor rotation 1 in cylinder 3 appropriate flow
regime was established, with the aim of creating the experiment conditions
closest to reality.
The experiments were performed in the following order [6]:
1) The sample surface smoothed to a surface roughness Ra no more than 1.6
microns in accordance with GOST 2789-73, then polished on felt circle GOI
paste and degreased with acetone. Degree of degreasing controlled by full
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wetting of the surface of the sample with distilled water. After degreasing, the
following operations were carried out with samples with tweezers.
2) For surface activation, the sample before test plunged for 1 min. into
water solution of 15% of mass hydrochloric acid then it was carefully washed
out flowing water and then the distilled water. The samples were then dried with
filter paper and kept in a desiccator with a desiccant dryer for 12 hours and were
weighed on analytical scales with a margin error no more than 0,0001 g.
3) The prepared witness samples were located in the device. Test time was
counted from the moment of placing the sample in corrosive environment; test
duration was 3; 6; 9 hours. Speed of the corrosion environment stream was 0,5
m/s according to GOST 9.905-82.
4) Immediately after test samples were subjected to visual inspection: the
presence of corrosion products and color is detected, and after removal of
corrosion products - the nature (type) of corrosion.
5) To determine the mass loss of samples their surface was cleared in
sequence:
a) friable corrosion products were removed with a spatula, brush and one of
the solvents: gasoline, kerosene or mineral spirits. In the presence of a dense
film from corrosion products their removal was carried out by the solutions
which aren't interacting with the main metal;
b) samples were washed with flowing water and then with distilled water,
dried with filter paper, degreased with acetone and packaged in filter paper, kept
in a desiccator with a desiccant dryer for 12 hours and weighed on an analytical
scales.
To recalculate the values of mass loss witness samples in value of the
corrosion rate used two indicators: the mass and depth.
Corrosion rate, expressed in terms of mass index Km (g/m2h), determined by
the formula (1):
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161
where m1 – mass of the sample before the test, g;
m2 – mass of the sample after the test, g;
S – the sample surface area, m2;
 – exposure time, hour.
Since the change in weight of the sample is directly proportional to the
penetration depth of corrosion in general corrosion rate is recalculated mass in
the deep index ПFe (mm / year), which describes the thinning of the sample per
unit time and determined according to the formula (2):
where 8760 – number of hours per year;
7,87 – iron density, g/sm3.
Results and discussion
The results of the mass and depth corrosion rate indicators obtained after
exposure witness samples in a corrosive environment for 3, 6 and 9 hours are
shown in Tables 3, 4, 5, respectively.
Table 3. Measurement results of the corrosion rate after 3 hours test
Sample
Sample mass
loss, g
Mass index of the corrosion
rate Кm, g/m2·h
Deep index of the corrosion
rate, ПFe mm/year
D1
0.0111
1.851238839
2.060591134
D2
0.0068
1.133842749
1.26206639
D3
0.0118
1.972487034
2.195551006
R1
0.017
1.514316858
1.68556743
R2
0.0142
1.283345973
1.428476585
R3
0.0202
1.829495339
2.036388713
RS1
0.0229
2.105483573
2.343587814
RS2
0.0213
1.942519133
2.162194105
RS3
0.0226
2.061324192
2.294434552
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162
The data in Table 3 show that sample RS-1 was subjected to corrosion at the
greatest rate, and sample D-2 was subjected to corrosion at the least rate;
samples RS-1-3 average were more sensitive to corrosion.
Table 4. Measurement results of the corrosion rate after 6 hours test
Sample
Sample mass loss,
g
Mass index of the corrosion
rate Кm, g/m2·h
Deep index of the corrosion
rate, ПFe mm/year
D1
0.0146
1.217481398
1.355163539
D2
0.0158
1.320563353
1.469902792
D3
0.0112
0.933752853
1.039348791
R1
0.0276
1.229268979
1.368284149
R2
0.0297
1.342090683
1.493864597
R3
0.0321
1.453633673
1.618021725
RS1
0.0311
1.418130166
1.578503208
RS2
0.0314
1.43198185
1.593921348
RS3
0.0323
1.484871602
1.652792279
From the received results in table 4 it follows that the sample of RS-3 was
subjected to corrosion at the greatest rate, and sample D-2 was subjected to
corrosion at the least rate. Also as well as after three-hour endurance of samples
in the corrosion media, samples RS-1-3 average were more sensitive to
corrosion.
Table 5. Measurement results of the corrosion rate after 9 hours test
Sample
Sample mass loss, g
Mass index of the corrosion
rate Кm, g/m2·h
Deep index of the corrosion
rate, ПFe mm/year
D1
0.0179
0.995110367
1.107645084
D2
0.0152
0.844824009
0.940363192
D3
0.0222
1.236983394
1.37687097
R1
0.0331
0.982821333
1.093966313
R2
0.0351
1.05740478
1.176984228
R3
0.0384
1.159284176
1.290384927
RS1
0.0478
1.464950724
1.630618595
RS2
0.0382
1.16125557
1.292579262
RS3
0.0429
1.304289201
1.451788234
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Analysis of data in Table 5 showed that the sample RS-1 was subjected to
corrosion at the greatest rate, and sample D-2 was subjected to corrosion at the
least rate; samples RS-1-3, as in previous experiments showed a higher
sensitivity to corrosion.
On the basis of data in tables 3-5 diagrams of corrosion rates dependence on
the sample witness type and tests time were made (Figures 4,5).
Figure 4. Dependence of mass index of corrosion rate on the witness sample
type and tests time
Figure 5. Dependence of deep index of corrosion rate on the witness sample type
and tests time
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From the figures 4 and 5 it follows that RS samples in comparison with D
and R samples show greater tendency to corrosion.
It is known that the corrosion destructions mechanism of welded joints
essentially doesn't differ from the destructions mechanism of the base metal.
However welded joints represents difficult, non-uniform, thermodynamic
unstable system which heterogeneity is caused by distinction of a chemical
composition, structures of separate zones, connection geometry, residual stresses
and plastic deformations in connection with uneven heating and cooling when
welding [7,8]. Therefore, the welded joints are characterized by increased macro
and micro electrochemical heterogeneity in comparison with the base metal.
Welded connections can be considered as a combination of a multi electrode
element with macro electrodes, such as seam, overheat zone, recrystallization
zone, main metal. Summary corrosive effect in each zone of the welded joint is
determined by corrosion losses due to: a) work of macro corrosion elements and
b) self-dissolution of each zone, i.e. the corrosion caused by work of micro
corrosion couples and dissolution on the homogeneous mechanism and the
corresponding zone. Depending on the degree of inhomogeneity of the weld (in
structure, chemical composition, etc.) and corrosive conditions will prevail one
or other corrosion mechanism [9].
Macro galvanic corrosion cells, weld - the main metal, for various
established electrochemical potentials can be divided into three groups [10]:
1) potentials of the base metal and weld almost identical, in this case macro
galvanic couple doesn't function, and corrosion of various zones is defined by
self-dissolution;
2) potential of the weld metal more negative than the base metal therefore
weld corrodes more intensively as a result of anode dissolution;
3) potential of the weld metal is more positive than the base metal, wherein
the base metal collapses more strongly.
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Thus, existence of additional source of internal stresses inside the RS
sample, such as weld, makes monitoring with its use as close as possible to the
actual conditions.
Conclusion
As a result of carried out tests it is founded that shape of witness samples
doesn’t influence essentially on the effectiveness of corrosion monitoring.
However, rectangular coupons with additional residual internal stresses in the
form of weld are exposed to corrosion at greater rate in comparison with
rectangular and disk-shaped coupons made from entire metal. Use of such
samples with the weld will provide more effective corrosion monitoring of the
welded technological equipment primarily exposed to corrosion.
References
1
Bradford S.A. Corrosion control. Edmonton: CASTI, 2001. 485 p.
[in English].
2
ASM Metals Handbook. Volume 13 Corrosion. L.J. Korb, D.L. Olson.
Houston: ASM International, 1987. 3455 p. [in English].
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Burlov V.V., Altsyibeeva A.I., Parputs I.V. Corrosion protection of
refinery equipment. Petersburg: HIMIZDAT, 2005. 248 p.[in Russian].
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Sukhotin A. Corrosion and protection of chemical equipment. Volume
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[in Russian].
5
Ahmad Z. Principles of corrosion engineering and corrosion control.
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6
GOST 9.506-87. Corrosion inhibitors of metals in water-petroleum
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1988. 17 p. [in Russian].
7
Vinokyrov V., Grigoriants A. Theory of welding strains and stresses.
Moscow: Engineering, 1984. 280 p. [in Russian].
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8
Zemzin V., Shron R. Heat treatment and welds properties. Petersburg:
Engineering, 1987. 369 p. [in Russian].
9
Logan G. Corrosion of metals under stress. Moscow: Metallurgy, 1970.
340 p. [in Russian].
10
Breinshtein M., Zaimovsky M. Mechanical properties of metals.
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Список используемых источников
1
Bradford S.A. Corrosion control – Edmonton: CASTI, 2001. 485 p.
2
ASM Metals Handbook. Volume 13 Corrosion / L.J. Korb, D.L. Olson.
Houston: ASM International, 1987. 3455 p.
3
Бурлов В.В. Альцыбеева А.И., Парпуц И.В. Защита от коррозии
оборудования НПЗ. СПБ.: ХИМИЗДАТ, 2005. 248 с.
4
Коррозия и защита химической аппаратуры / под ред. А. М.
Сухотина, А.В. Шрейдера, Ю.И. Арчакова. М.: Химия, 1974. Т. 9
Нефтеперерабатывающая и нефтехимическая промышленность. 576 с.
5
Ahmad Z. Principles of corrosion engineering and corrosion control -
Amsterdam: Elsevier Science & Technology Books, 2006. 660 p.
6
ГОСТ 9.506-87. Ингибиторы коррозии металлов в водно-нефтяных
средах. Методы определения защитной способности. Введ. 1988-01-07. М.:
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167
About the authors
Сведения об авторах
A.P. Efremenko, Master Student of MTP 21-12-02 Group of the Chair «Oil
and Gas Technology» FSBEI НРЕ USPTU, Ufa, the Russian Federation
Ефременко
А.П.,
магистрант
группы
МТП
21-12-02,
кафедра
«Технология нефти и газа» ФГБОУ ВПО УГНТУ, г. Уфа, Российская
Федерация
A.Y. Spaschenko, Candidate of Engineering Sciences, Head of Refining
Process Laboratory LLС “R&D Center Salavatnefteorgsyntez”, Salavat, the
Russian Federation
Спащенко А.Ю., канд. техн. наук, начальник лаборатории процессов
нефтепереработки
ООО
«Научно-технический
центр
Салаватнефтеоргсинтез», г. Салават, Российская Федерация
I.F. Sadretdinov, Candidate of Chemical Sciences, Head of Problem
Research Laboratory LLС “R&D Center Salavatnefteorgsyntez”, Salavat, the
Russian Federation
Садретдинов
проблемных
И.Ф.,
канд.
исследований
хим.
ООО
наук,
начальник
лаборатории
«Научно-технический
центр
Салаватнефтеоргсинтез», г. Салават, Российская Федерация
e-mail: [email protected]
K.V. Aleksandrova, Candidate of Engineering Sciences, Leading Specialist
of Refining Process Laboratory LLС “R&D Center Salavatnefteorgsyntez”,
Salavat, the Russian Federation
Александрова К.В., канд. техн. наук, ведущий специалист лаборатории
процессов
нефтепереработки
ООО
«Научно-технический
центр
Салаватнефтеоргсинтез», г. Салават, Российская Федерация
© Electronic scientific journal "Oil and Gas Business". 2014. №3
http://www.ogbus.ru