684 Zhao, Teng, Yang and Tan
Corrosion inhibition approach of oil production
systems in offshore oilfields
Synthesis and modification of imidazoline were carried out based
on review of the corrosion inhibitor development and application
for oilfields. A series of imidazoline compounds were synthesised
through the solvent dewatering and vacuum dewatering methods.
After reaction of imidazoline with ethane oxide, the produced com-
pound was used to react with halogen hydrocarbon and polypho-
sphoric acid respectively. Finally an agent with performance of cor-
rosion-inhibition, sterilisation and anti-scaling was obtained. The
structures of the compounds were characterised by the Fourier
transformation infrared spectrum. The relationships between corro-
1 Introduction
Corrosion is a tricky problem in raw oil development and
production. Oil companies have expensed a huge amount of
money to solve this problem every year all over the world.
Disasters like economical losses, casualties and environmen-
tal side effects caused by corrosion, however, still take place
frequently. The cost due to corrosion alone in the UK was
£ 13.65 billion in 1969; it’s $ 170 billion by corrosion in
the USA in 1992 [1]. Corrosion affects between a quarter
and a half of all potable water mains, especially old ones
in cast iron or uncoated steel in France [2]. Corrosion resulted
in 3% economical loss of the GDP in China; 30
40% of the
economical loss could be avoided if anti-corrosion measures
were taken properly [3]. Leakage and spills of oil distribution
pipes due to corrosion can cause serious environmental pollu-
tion. Therefore, it is significant to study the corrosion mechan-
ism and its prevention and mitigation methodology. Good re-
search and development on corrosion can be useful for envir-
onmental and ecological protection, improve security of de-
velopment and production and avoid great economic loss
for oil companies. There are many factors that cause corrosion
of the oil production systems, the most important ones are hy-
drogen sulphide, carbon dioxide [4] and bacteria [5, 6].
* L. Zhao, X. Tan,
School of Environmental Science and Engineering, Tianjin Uni-
versity,
Tianjin 300072 (P.R. China)
H. K. Teng,
Tianjin Intitute of Chemical Engineering,
Tianjin 300076 (P.R. China)
Y. S. Yang,
School of Civil Engineering, Queens University Belfast,
Stranmillis Road, Belfast BT9 5AG (UK)
DOI: 10.1002/maco.200303789
Materials and Corrosion 2004, 55, No.
L. Zhao*, H. K. Teng, Y. S. Yang and X. Tan
sion inhibition effectiveness of the compounds and their structures
were investigated so as to determine the structure of a novel corro-
sion inhibitor. The selected corrosion inhibitor was evaluated by a
series of experiments to understand the characteristics of imidazo-
line derivative and some major factors associated with oil produc-
tion in the oilfields of China. The experimental results showed that
this corrosion inhibitor has outstanding performance of corrosion
inhibition and sterilization, and is suitable for corrosion inhibition
of the oil abstraction systems with high water-content in the off-
shore oilfields.
The oil abstraction in offshore oilfields often use sub-
merged pumps involved with shorter separation of oil, gas
and water, higher circulation and worse corrosion compared
with inland oilfields. The corrosion is particularly serious
when CO2, H2S and sulphate reducing bacteria (SRB) are in-
volved in the offshore oilfields. Table 1 shows corrosive per-
forations of the oil abstraction systems in an offshore oilfield,
China between January 1996 and May 2000. Corrosion per-
foration caused by bacterial and acid agents is a major issue,
account for 70%, according to the five years sampling and
investigation. Fig. 1 shows the typical appearance of the cor-
rosion. Such a corrosive phenomenon is rather common in the
offshore oilfields of China. A feasible and practical solution
for such corrosion prevention is needed.
In the anti-corrosion measures under the offshore oilfield
condition, corrosion inhibition is one of the most effective
methods for metal equipments. Inhibitor study was started
in 1940s; it included mainly inorganic salts and small-mole-
cular inorganic compounds. With research and development
of the corrosion inhibitors, organic compounds were becom-
ing more and more popular due to their low cost, multi-roles in
one agent and surface retention reduction [7]. Many inhibitors
such as quaternary ammonium salts of imidazoline and poly-
vinylmeyhyl diamine, imidazoline derivative, organic amine
and organic phosphate have been developed and applied
widely [8, 9]. These inhibitors were effective to corrosion
in the earlier stage; however, with change of oil abstraction
technology, variation in water quality and content of abstrac-
tion liquid in the oilfields, improved inhibitors suitable for
modern, higher-water content oilfields with better water-solu-
bility, low emulsifying tendency and more effective anti-cor-
rosion are timely needed. This paper presents a systematic re-
search on corrosion prevention of the oil abstraction systems
and oil-water separating systems in offshore oilfields. A fea-
sible and practical method was proposed to develop a new cor-
rosion-inhibiting and bactericidal agent by improving imida-
zoline compound. The structure-effectiveness, inhibiting re-
sult and evaluation of the new corrosion inhibitor were inves-
tigated and discussed for corrosion prevention in the offshore
oilfields.
F 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Materials and Corrosion 2004, 55, No. 9
Table 1. Corrosive perforation of the abstraction systems in an offshore oilfield (China)
No. Corrosion factors Corrosion locations
1 Bacteria (SRB) Production and discharge pipelines
2 H2S and acid Under-sea spin flow implement pipe and washing pipeline
3 Oxygen Surface discharge pipeline
4 Dissolved salts Pipeline in seawater
5 Gases Descending discharge pipes
6 Others Steam pipes and domestic pipelines
Fig. 1. Typical feature of the corrosion
2 Materials and methods
2.1 Equipments and materials
The equipments used in this study include an EQUINOX55
Fourier infrared spectrometer, a M351 corrosometer, 721
spectrophotometers, PH-201 acid meters, TG328A analytical
and TN tray wrest scales, DL-10101B galvanothermy blast
dry boxes, HH-S constant temperature path pans, ZX-4 va-
cuum pumps, and many other necessary instruments. Chemi-
cal reagents of ethylenediamine, di-ethylenediamine, butyric
acid, capric acid, cherry bay acid, palm acid, oleic acid, stearic
acid, chloropropane oxide, ethane oxide, propenal, dimethyl-
benzene, toluene, acetone, nitrate, sulphourea, phosphorus
acid, methanol, ethanol, muriatic acid, ammonium chloride,
potassium hydroxide, sodium hydroxide and hexadecanol so-
dium sulphate were used for the research and development.
The corrosion materials are A3 steel slices and electrodes:
Fe 99.32%, C 0.18%, Mn 0.45%, S 0.02% and P 0.013%.
Imidazoline compound was synthesised by using the sol-
vent dewatering and vacuum dewatering methods. The experi-
ments can be described as following procedure: putting 1
gram-molecule oleic acid (281 g) in a flask installed with ther-
mometer, capillary and decompression distillation settings;
adding and mixing up slowly 1 gram-molecule di-ethylene-
diamine (99 g), a heat-giving-up process during the addition;
withdrawing air in the flask and injecting nitrogen, continu-
ously heating up to 140
170 8C and keeping 1 hour, then
slowly decompressed and distilled dewatering for 2
3
hours. When about 1 gram-molecule water (18 g) was ob-
tained by a water separator, the dewatering process became
slower. Heating again up to 180
210 8C, decompressed
and distilled dewatering for 5
6 hours, further 1 gram-mo-
lecule water (18 g) was obtained. When finished dewatering,
Corrosion inhibition approach of oil production systems 685
Perforation times Ratio (%)
108 56.6
27 14.1
7 3.7
6 3.1
10 5.2
33 17.3
dropping down temperature slowly, a palm red glue-like com-
pound was obtained finally.
To synthesise imidazoline derivative, the obtained ami-
noethyl imidazoline compound was reacted with ethane oxide
to produce polyoxethyl imidazoline compound and then re-
acted with chloropropane oxide to produce a corrosion-inhi-
biting and bactericidal agent, which was further reacted with
multi-phosphate acid to create a scale-inhibiting agent. The
detailed process of synthesis was: adding 0.1 gram-molecule
polyoxethyl ether-aminoethyl imidazoline (EMM) compound
(47.6 g) and 1 gram-molecule methanol (32 g) into a three-en-
trance flask installed with thermometer and circumfluence
settings; slowly whisking and adding 0.1 gram-molecule
(9.25 g) chloropropane oxide; gradually heating up to
60
70 8C and keeping reaction for 6
8 hours; cooling ma-
terials to 50 8C after that, and adding pure ethanol; finally the
compound with red-palm colour was obtained.
2.2 Structure and effectiveness
The structure of the synthesised imidazoline compound was
characterised by the Fourier transformation infrared spectro-
meter. The characteristics of the novel corrosion and bacter-
ium inhibitor were identified through investigating the rela-
tionship between the structure of imidazoline derivative
and its performance of corrosion and bacterium inhibition.
The corrosion inhibiting efficiency of the developed imidazo-
line inhibitor was evaluated by the weight loss method. The
bactericidal effect of the corrosion inhibitor was also mea-
sured with the SRB test ampoule. Further evaluation and tests
were carried out and the obtained inhibitor was also applied in
an offshore oil field (reported elsewhere), which demonstrated
a practical, reliable and effective corrosion inhibiting and bac-
tericidal performance.
3 Results and discussion
3.1 Structure of imidazoline compound and inhibition
The structure of imidazoline compound was identified by
the infrared spectrometer, and the wave number was
400
4000 cm1. The infrared spectrum is shown in
Fig. 2. As illustrated by the figure, there are apparent absorb-
ing peaks at 1610, 1650 and 3294 cm1 respectively. These
indicate double bond N¼C-N stretch vibration peak, C¼N
bond stretch vibration absorbing peak and N-H stretch vibra-
tion absorbing peak of the molecules. Therefore, imidazoline
compound belongs to pentaimidazolinium compounds.
686 Zhao, Teng, Yang and Tan Materials and Corrosion 2004, 55, No. 9

Table 3. Effect of the hydrophilic ethylene amine chain lengths on

corrosion inhibition

Ethylene Corrosion Corrosion Inhibiting rates

amine number rates rates (oleic acid, %)
(capric (oleic acid,
acid, mm/a) mm/a)
0 5.18 5.16 76.25
1 4.65 4.79 76.68
2 4.27 4.33 80.42
3 4.38 4.45 79.92

Fig. 2. Infrared spectrum of imidazoline compound 5 5.61 6.3 74.28

None 21.81 21.81 n/a
Table 2. Effect of the hydrophobic carbon chain lengths on corro-
sion inhibition

Atomic number of Corrosion rates Inhibiting rates capric acid and oleic acid respectively by reacting with ethy-
hydrophobic carbon (mm/a) (%) lene amine. Their general molecular formula is
3 (butyric acid) 9.37 57.04 C17 H33  C ¼ N  CH2
9 (capric acid) 4.79 78.04 j j
N  CH2
11 (cherry bay acid) 6.11 71.98 j
14 (palm acid) 5.84 73.22 ðCH2 CH2 NH2 Þn H
17 (oleic acid) 4.65 78.68 The wastewater from the same oilfield and 30 mg/l medi-
None 21.81 n/a cament were used to evaluate the effectiveness of the hydro-
philic ethylene amine compounds by a similar approach. The
experimental results are shown in Table 3, which indicate that
appropriate number of ethylene amine in the imidazolinium
The structure of imidazoline compound is closely related to compounds is 1
3; i.e., it is better to use diethylene triamine,
its inhibition effectiveness. In order to identify such relation- triethylene tetraamine, tetraethylene pentamine to synthesise
ships, a series of imidazoline compounds synthesised by var- the imidazolinium compounds. When the ethylene amine
ious carbon-chain carboxylic acids, such as butyric acid, cap- chain is too long, water-solubility of the compounds will de-
ric acid, cherry bay acid, palm acid and oleic acid, and diethy- crease which results in a density decrease of the hydrophobic
lenetriamine, were evaluated. Effect of the carbon chain radicals ranked on metal surface and thereby affects the cor-
lengths of the imidazoline molecules on corrosion inhibition rosion inhibition effectiveness.
was also investigated (Table 2). The general molecular struc-
ture of the imidazoline compounds with various carbon chain
lengths can be described as: 3.2 Structure of imidazoline derivative and bactericidal
effectiveness
N  CH2
k j The structure of imidazoline derivative was also identified
R  C  N  CH2 by the Fourier transformation infrared spectrometer with
j wave numbers of 400
4000 cm1. The obtained infrared
CH2 CH2 NH2  spectrum is shown in Fig. 3. There are two strong absorbing
peaks at 1072 and 1123 cm1, demonstrating the molecular
To simulate the corrosion of wastewater from an offshore structures of C-O-C and C-OH groups. The strong absorbing
oilfield in China, the chemical medicament of 30 mg/l was peak at 1644 cm1 indicates O¼H double bond structure; the
used. The inhibiting effect of O2 removal by CO2 was carried one at 3357 cm1 is O-H stretch vibration absorbing peak. Ti-
out in 48 hours under closed condition with constant pressure tration analysis with hexadecanol sodium sulphate and silver
0.05
0.06 MPa and temperature 50 8C. The results are nitrate confirmed that there were quaternary ammonium radi-
shown in Table 2. From the data in the table, corrosion inhibi- cal and chlorine ion in the compound molecules. The synthe-
tion is most effective when the R radical atomic number in the sised compound is therefore determined as quaternary ammo-
imidazolinium compounds is 8 – 10 or more than 15. Corro- nium salt compound.
sion inhibition is more effective when the imidazolinium com- To study the relationship between the structure of imidazo-
pounds containing double bond in R radical than those without line derivative and its bactericidal effectiveness, various imi-
double bond with same carbon chain lengths. Experiments dazoline derivatives were synthesised by reactions between
also demonstrated that not only the carbon chain lengths of polyoxethyl ether-aminoethyl imidazolinium compound
the compounds affected corrosion inhibiting effectiveness, (EMM) and chloropropane oxide, chlorinated benzyl and
but also the chain length of ethylene amine would do (see Ta- chloroacetic sodium respectively. The synthesised com-
ble 3). The imidazolinium compounds were synthesised by pounds, named as EMM-E, EMM-B and EMM-A accord-
Materials and Corrosion 2004, 55, No. 9 Corrosion inhibition approach of oil production systems 687

Table 5. Comparison of the bactericidal effect

Compounds Bactericidal rates (%)

EMM-E 99.0
EMM-B 90.0
EMM-A 90.0

Table 6. Relationship between HS-608 amounts and corrosion in-

hibition

HS-608 5 10 20 30 40 None
amounts (mg/l)
Fig. 3. Infrared spectrum of the quaternary ammonium salt com-
pound Corrosion 8.13 4.84 2.07 1.29 24.91
rates (mm/a)

ingly, underwent bactericidal experimental evaluation. The Inhibition 67.4 80.6 91.7 94.8 96.3 n/a
rate (%)
bacterial SRB was cultured from the wastewater of the oil-
field, and the medicament concentration was 100 mg/l. The Surface black black greyish gloss gloss black
water quality of the oilfield (D06) in China is shown in Table 4 condition black
and the experimental results are shown in Table 5. Results in-
dicate that EMM-E has best bactericidal effectiveness and is
promising in application to the oilfield. A new corrosion in- Table 7. Change of corrosion inhibition with temperature
hibitor, HS-608, was made from the EMM-E compound for Temperature (8C) 50 60 80
better corrosion inhibiting and bactericidal purposes.
Corrosion rates (mm/a) 1.29 1.74 2.11

3.3 Inhibition evaluation Inhibition rate (%) 94.8 93.0 91.5

Surface condition gloss gloss gloss
According to the analysis of the corrosion factors in the oil-
field, inhibition effectiveness of the new imidazoline inhibitor
was evaluated against H2S, CO2 and bacterial corrosion.
3.3.2 Evaluation of dynamic acid-corrosion inhibition

3.3.1 Evaluation of static acid-corrosion inhibition
The above oilfield water (D06) was taken to evaluate the
new corrosion inhibitor, HS-608. Various amounts of HS-
608 were investigated through removing O2 by CO2 under sta-
tic conditions of 50 8C, 48 hours, constant pressure of
0.05
0.06 MPa. The experimental results are shown in Ta-
ble 6. The larger the concentration of HS-608 is, the more ef-
fective corrosion inhibition will be. A satisfactory result was
achieved when it was 20 mg/l; however, 30 mg/l would be
more reliable with consideration of complicated reality and
higher security. Another experiment was carried out to inves-
tigate the relationship between temperature and corrosion in-
hibition of HS-608 using the weight-loss test. Similar condi-
tions were used: D06 oilfield water, O2 removal by CO2, 48
hours and constant pressure 0.05
0.06 MPa. The results are
shown in Table 7. The test results indicate that the effective-
ness of HS-608 is slightly reduced with increase of tempera-
ture. However, it has a satisfactory corrosion inhibition within
a temperature range of 50
80 8C.
The D06 oilfield water was taken to evaluate the inhibitor
HS-608 under dynamic flow condition, lower flow rate
110
130 and upper rate 230
250 revolutions per minutes
(rpm). The removal of O2 by CO2 was carried out with 30 mg/l
HS-608 concentration in a closed system, under conditions of
constant pressure of 0.05
0.06 MPa, temperature at 50 8C
and 48 hours duration. The experimental results are shown
in Table 8. The flow rate demonstrates a minor influence
on corrosion inhibition; HS-608 exhibits a satisfactory corro-
sion inhibition under the tested flow-rates, which meets the
corrosion inhibition requirement of the oil abstraction systems
in offshore oilfields.
3.4 Inhibiting mechanism of HS-608
The imidazoline inhibitors contain both hydrophobic long
carbon chain groups and hydrophilic groups. In acid solution,
the positively charged quaternary ammonium radicals in the
hydrophobic groups can produce absorption in the cathodic

Table 4. In-situ sampling and analysis results in the oilfield for D06 water. All in mg/l except pH; SRB are in numbers per ml.

Naþ/Kþ Mg2þ Ca2þ Cl SO2

4 HCO
3 CO2 pH H 2S Fe TDS SRB

14 200 385 1890 25 900 388 291 51.9 6.0 8.0 2.0 43 100 1.5  106
688 Zhao, Teng, Yang and Tan Materials and Corrosion 2004, 55, No. 9

Table 8. Evaluation of acid-corrosion inhibition under dynamic flow condition

Samples Reference HS-608 None

Flow rates (rpm) 120 240 120 240 120 240
Corrosion rates (mm/a) 3.99 4.87 3.07 3.65 34.87 37.36
Inhibition rate (%) 88.6 87.0 91.2 90.2 n/a n/a
Surface condition greyish black greyish black gloss gloss black black

areas on the metal surface; the hydrophobic groups of the mo-
lecules contain N, O and P elements with lone pair electrons,
which can hybridise with d orbit in the metal elements and
form a firm chemical adsorptive layer. It thus prevents Hþ
from contacting the metal surface, inhibits reduction of Hþ
and thereby inhibits metal corrosion.
The experiments demonstrated that the main chain in the
long chain imidazolinium alkyl in acid media possesses a
good corrosion inhibition performance. The branch chains
of the alkyl chains can reduce inhibition because such branch
chains can inhibit close occluding of the chains. The inhibition
can be improved if molecules have duel-, tri-chains and ben-
zene chains in the modification.
The quaternary ammonium radicals possess strong electron
attraction, which constrains the electron movement on the me-
tal surface, relieves hydrogen release at the cathode and inhi-
bits anode dissolution. Imidazoline derivative thus hinders
formation of hydrogen atoms required for SRB activity so
that the common SRB corrosion in oilfields is inhibited.
The quaternary ammonium radicals of imidazoline compound
act on the cell membrane of SRB effectively and inhibit en-
zyme activity; whilst the hydrophobic and fat-like groups can
dissolve lipid on the membrane resulting in perforations and
breakage of the cell walls and sterilisation.
5 References
[1] ASM, ASM Handbook: Corrosion.Vol.13, ASM International,
USA 1992.
[2] EEP, A quarter of water mains in France are affected by corro-
sion. Newsletter of the European Environmental Press, April 1,
2003 – issue 43. http://www.eep.org/.
[3] B. M. Wei, Theory and Application of Metal Corrosion. Che-
mical Engineering Press, Beijing, China 2001.
[4] A. N. Markin, Protect. Metals 1995, 31, 359.
[5] A. A. Efimov, B. A. Gusev, O. Y. Pykhteev, V. V. Martynov, I.
N. Orlenkova, I. V. Miroshnichenko, S. Y. Bakhir, S. I. Emelin,
Protect. Metals 1995, 31, 550.
[6] J. C. Tardy, P. Caumette, R. Matheron, C. Lanau, O. Arnauld,
M. Magot, Canad. J. Microb. 1996, 42, 259.
[7] G. M. Rahmatullina, E. L. Volodina, N. V. Miasoedova, T. A.
Zuyeva, F. V. Sharafutdinova, G. N. Zapeklaya, Neftyanoe Kho-
zyaistvo 2000, 11, 36.
[8] Y. K. Huang, J. S. Zhen, Proceedings of the 11th National Semi-
nar on Corrosion Inhibition 1999, Shenzhen, China (in Chi-
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[9] A. Al-Sayegh, Y. Carew, A. Al-Hashem, Anti-Corr. Meth. Ma-
ter. 2001, 48, 245.
(Received: December 19, 2003) W 3789

4 Conclusions

Based on investigations on the structures of the corrosion

inhibitors and their relationships to the corrosion inhibition
effectiveness, an imidazoline derivative was selected as the
most suitable corrosion inhibitor against acid and SRB bacter-
ial corrosion of the oil abstraction systems in the high-water
content oilfields. Through a series of experiments and char-
acterisation, a new corrosion inhibitor, HS-608, was synthe-
sised from imidazoline derivative. The evaluation of static and
dynamic acid-corrosion inhibition showed that the inhibitor
HS-608 is very effective to H2S and CO2 corrosion in the
oil production systems of oilfields; the inhibition rate obtained
from the experiments is greater than 90%. This inhibitor is
also effective to the sulphate reducing bacterial corrosion;
the bactericidal rate is over 90%. In-situ application of the in-
hibitor HS-608, presented in other materials, also demon-
strated reliable and effective anti-corrosion performance.