UNIVERSIDAD NACIONAL DE INGENIERIA

FACULTAD DE INGENIERÍA DE PETRÓLEO, GAS NATURAL Y

PETROQUÍMICA

X FERIA Y CONCURSO DE PROYECTOS

Biological corrosion inhibitor in oregano-based acid medium

for mild steel pipes
Atoche K., Gamarra J., Guzmán A., Ramos W.
atochec@fip.uni.edu.pe, jgamarrar@fip.uni.edu.pe, aguzmanl@fip.uni.edu.pe, wramos@fip.uni.edu.pe
Corrosión, Sección A

Abstract: The present research paper studies the obtaining of a biological corrosion inhibitor using oregano,
and its objective is to determine the efficiency of this inhibitor in the prevention of corrosion of mild steel in
acidic medium (HCl), since steel is a metal widely used in the hydrocarbon industry. The experiments that the
efficiency of said inhibitor increases, by increasing the concentration in the acid medium reaching results of
36% with inhibitor concentrations of 429.37 ppm in a corrosive HCl medium at 1.03 M and the appearance of
the metals is then analyzed of the corrosion test, observing a pitting corrosion in the case of steel with inhibitor,
and a generalized corrosion in steel without inhibitor. It was concluded that oregano-based corrosion inhibitor
is effective for mild steel.

Keywords: Oregano; mid steel corrosion; acidic HCl medium.

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1. INTRODUCTION
During the twentieth century, mild steel has
escalated widely in the industry as an important
material in the construction of a large number of
metal structures for application in crude oil and
natural gas refineries, petrochemical units, civil
constructions and agriculture [1].
Although mild steel has great advantages such
as low prices, good malleability, formability and
surface hardness, its low corrosion resistance
remains a challenging and problematic concern. In
other words, corrosion in mild steel structures such
as storage tanks, ships, water injection systems
utilizing units in many industries in contact with
solutions containing chloride, that is, seawater has
remained as a serious problem wasting considerable
financial resources per year [1]. That is why
corrosion prevention of structures of this type of
steel remains a major concern among corrosion
scientists [2]. On the other hand, the hydrochloric
acid (HCl) solution is part of many industrial
processes, such as steel pickling, acidification of oil
wells, leather processing, production of organic and
inorganic compounds and industrial cleaning [3].
Corrosion is the normal and inevitable
phenomenon where deterioration of metallic
materials occurs as a result of chemical, physical
and biological attack of these upon contact with
their environment [4]-[5]. This almost always
occurs through an electrochemical reaction, which
is characterized by the exchange of electrons
through oxidation and reduction reactions [6]. One
of the most common mechanisms of corrosion in
aqueous environments is the flow of electricity from
certain areas of the metal surface to other areas
through an electrolyte, which can be from fresh or
salt water to the strongest alkali or acid. The term
anode is used to describe that portion of the metal
surface that is corroded and the term cathode is used
to describe the metal surface from which the current
leaves the solution and returns to the metal. [6]-[7].
The intensity of the deterioration depends on many
factors such as: mechanical characteristics of the
metal (stainless steel lasts longer than a normal
steel), aggressive agents (acids corrode more than
alkalis in steels), temperature (a higher temperature
causes a higher wear), flow velocity (water or air
currents at high speeds also accelerates the level of
corrosion) [4], [7].
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Corrosion of metals is a very important problem
in any industry, since it is estimated that the annual
global cost to mitigate this problem is $2.5 billion,
while in the US alone, corrosion expenditures in the
oil and natural gas industry amount to about $ 26.8
billion/y (Figure 1) [5]. In 1955 the oil company,
British Petroleum (BP) conducted an economic
study of its operations in the North Sea, where it
estimated that the expenditures for corrosion
prevention and control amounted to about 8% of
capital expenditures total for your projects. On the
continental shelf of the United Kingdom, between
25% and 30% of BP's operating costs corresponded
to corrosion control and management. In addition to
direct costs, the study also determined that
corrosion had a significant indirect effect associated
with health, safety and environmental problems [8].
Refining Distribution
3.7 5.0
Production
Production
1.4
1.4
Storage
7.0
Driving lines
Ships and 7.0
tanks
2.7
Figure 1. Disbursements for corrosion in the oil and natural
gas industry in the US, expressed in billions of USD/year.
Source: Own elaboration based on [8]
To control the corrosion of steel, several types
of protection techniques have been introduced, such
as coatings, cathodic protection and corrosion
inhibitors. Most of these methods are not applicable
for delaying corrosion of metals in acid solution.
[9]. However, corrosion inhibitors are very efficient
in acid medium, which is why they are considered
the first line of defense against corrosion in the oil
processing and extraction industries. These are
commonly added in small quantities to acidic
environments, such as in cooling waters, steam and
many other environments, either continuously or
intermittently, reducing the intensity of corrosion
[10].
Although corrosion inhibitors are very useful to
avoid economic losses, there are environmental
problems associated with the application of most of
25, Perú
these, since some are toxic to the ecosystem [11].
The 21st century has witnessed huge research
activities on natural products in corrosion, and it has
been found that plant extracts, in addition to being
ecological, are also economically viable and easily
accessible. In fact, it has been found that bioactive
compounds in plant extracts are as effective as
synthetic inhibitors [5]. Plant extracts used as
corrosion inhibitors range from mint, mustard,
artemisia, pepper, barley to oregano [5], [12].

Oregano extract is a reliable inhibitor and gives

good results of corrosion inhibition in strong media
such as hydrochloric acid, Table 1 shows the
efficiency of the inhibitor at different concentrations
of inhibitor in a 1M HCl solution [11].

Table 1. Oregano inhibitor efficiencies at different

concentrations in 1 M HCl.
Concentration
n% Corrostion rate
(mg/L)
Blank (1M) 95.30
400 59 39.00
600 74 25.07
800 82.45 16.70 Figure 2. Organic compounds present in oregano that
1000 91.22 8.35 allows to inhibit corrosion.
1200 93.38 6.24 Source: Own elaboration based on [12]
Source: Own elaboration based on [11]
Oregano leaves (origanum vulgare) were
In the present work, oregano extract at a purchased at the Central Market located in Lima.
concentration of 1500 mg / L will be used as a Then, 375.7 mg of oregano in 250 mL of deionized
corrosion inhibitor for a mild steel surface in acidic water was added. The solution went through a
medium at a concentration of 1M, and the degree of reflux process for 6 hours. After this time, it was
corrosion will be determined by the method of allowed to cool for 10 minutes and then filter the
percentages of mass loss. extract of the oregano leaves in the solution and
pack it in a closed bottle [12].
2. MATERIALS AND METHODS

2.1. Inhibitor Preparation

It is important to know that the oregano-based

corrosion inhibitor works thanks to its active
components, Carvacrol and Thymol, special organic
groups that have heteroatoms (oxygen) which form
a protective layer, since they are electron-rich
groups that can donate the single pair of electrons to
metal ions, that is, Fe2+, which have empty 3d
orbitals [2], [12].

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 and the density of the metal was measured using the
thrust principle, which was equal to 7.6964 g/cm3.

Figure 5. Preparation of the metal for corrosion tests.

Source: own elaboration

Figure 3. Schematic preparation process of the green
Tamarindus extract inhibitor that was used as a mild steel
corrosion inhibitor.
Source: own elaboration
2.2. Acid medium preparation
The concentration of concentrated hydrochloric
acid was determined by an acid-base titration, which
was diluted to concentrations of 0.513 and 1.026 M
HCl in the corrosion tests.
2.4. Preparation of the metal for corrosion tests.
It was carried out in 6 closed containers, where
the metals were held with nylon wire (it is
anticorrosive) and different volumes of acid and
natural inhibitor were added. The bottles were
stored in an airtight space at a temperature of
approximately 22.5°C for 8 and a half days.

Figure 4. Acid-base titration and dilution.

Source: own elaboration

2.3. Preparation of mild steel simples

First, two mild steel bars were purchased from

the Bohler distributor, which were cleaned with
isooctane to remove excess grease that came from
the factory, then sanded and rinsed with distilled
water and cut into 6 slices (Figure 5) Finally, the Figure 6. Corrosion test of mild steel in acidic HCl medium
masses and dimensions of each were measured with at 22.5°C.
Source: own elaboration
an electronic scale and a Vernier ruler respectively
2.5. Corrosion Index Calculation

After 8 and half days, the mild steel samples

were weighed again and then the average mass loss
was calculated using equation 1:

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 Equation 1
Where W0 and W represent the initial and final
masses respectively of the samples. The corrosion
rate was determined by the equation 2 [15].
Similarly, in Figure 7 verify the sealed 100 ml
containers, where verify the corrosion test line for
the conditions shown in Table 3.

Equation 2
Figure 7. Sample containers
Where A (in2) is the surface area of the steel Source: own elaboration
sample, D (g/cm3) is the density of the metal and t
(days) is the time exposed to corrosion. In addition, the following characteristics of the
metals used in the present investigation were
Finally, the efficiency of the corrosion inhibitor obtained.
is obtained by the equation 3 [9]-[12]:
Table 3.Calculation of the MPY for each of the
corrosion tests for each mild steel plate.
Loss Densidity Time Area
MPY
Mass (g) (g/cm3) (days) (in2)
Equation 3 0.5941 7.6941 8.5 1.6069 0.1260
1.1078 7.6941 8.5 1.7141 0.2203
Where n is the efficiency of oregano-based 0.5271 7.6941 8.5 1.4462 0.1242
0.8287 7.6941 8.5 1.6605 0.1701
corrosion inhibitor, and MPY0 and MPY are
0.4742 7.6941 8.5 1.5534 0.1041
corrosion rates without inhibitor and inhibitor 0.6661 7.6941 8.5 1.6069 0.1413
respectively Source: self made

3. RESULTS AND DISCUSSION A curve is shown in Figure 8 that relates

mathematically how the MPY varies against the
3.1. Corrosion test results concentration of the inhibitor for concentrations of
hydrochloric acid at 0.513M and 1.026M.
Table 2 shows the results of inhibitor and acid
concentration, as well as the initial and final masses
of the metals at a time of 8 and half days. Likewise,
Figure 7 shows the sample container containers.

Table 2. Condiciones de operación en las distintas pruebas

de corrosión.
CHCl
(M) Initial
Cinhibitor Final weigh
Vol: weigh
(ppm) (g)
40 (g)
mL
0.513 0 15.3687 14.7746
1.026 0 14.5958 13.488
0.513 250.46 9.4617 8.9346 Figure 8. MPY Vs C inhibitor.
1.026 250.46 15.3720 14.5433 Source: Own elaboration
0.513 429.37 12.6713 12.1971
1.026 429.37 15.0205 14.3544 The results of the efficiency of corrosion tests
Source: own elaboration on activated carbon in HCl acid medium are shown
in the following table:

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Table 4. Efficiency results in the different However, as shown in the results, at a higher
corrosion tests. concentration in the acidic environment the oregano
CHCl acts with better inhibition properties.
(M) CInhibitor VolInh Efficiency
MPY 4. CONCLUSIONS
Vol: 40 (ppm) (mL) (n%)
mL
0.513 1502.8 10 0.1242 1.41%  It was concluded that oregano is a good
1.026 1502.8 10 0.1701 22.78% inhibitor at concentrations of more acidic
0.513 1502.8 20 0.1041 17.42% medium.
1.026 1502.8 20 0.1413 35.86%
Source: Self made  Oregano has a 36% efficiency of corrosion
Note: MPYAc 0.513=0.1260 & MPYAc 1.026=0.2203
inhibition at concentrations of 429.37 ppm in
On the other hand, a graph showing the an acid medium of 1.03 M concentration of
efficiency of the inhibitor against inhibitor HCl in relation to volumes from 1 to 3,
concentrations for hydrochloric acid concentrations respectively.
at 0.513M and 1.026M is presented in Figure 9.
 The mass loss rate per area and time of mild
steel in acidic acids of 0.51 and 1.03 M HCl
without inhibition is 0.1260 and 0.2203
respectively.

 It was concluded that the type of corrosion

caused by the acidic medium is of the bite
type while with the use of the oregano
inhibitor the effect was less like the type of
surface corrosion.

Figure 9. n Vs C inhibitor. Source:

Own elaboration

The effect of the test without inhibitor (a) and 5. RECOMMENDATIONS

with natural inhibitor (b) is shown in Figure 10.
Where it can be observed that in (a) pitting  Use a better method of extracting organic
corrosion occurs and in (b) widespread corrosion compounds from oregano, to obtain greater
occurs due to the effect of hydrochloric acid. inhibitor efficiency.

 Use other types of steel in different acidic

media to check the effectiveness of the
inhibitor
(a (b)
)  Use microscopic methods for a better
evaluation of the corrosion index.
Figure 10. Comparison between the test effect without
inhibitor (a) and with natural inhibitor (b)  It is recommended for future evaluation to
Source: own elaboration evaluate the efficiency of the inhibitor in a
continuous flow medium
3.2. Discussion
6. REFERENCES
Since a more sophisticated extraction method
was not worked and relatively low concentrations of [1] S. A. Haddadi, E. Alibakhshi, B. Ghasem, B.
natural inhibitor were obtained from oregano, the Ramezanzadeh, and M. Mahdavian, “A
desired results were not obtained.
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 detailed atomic level computational and [11] H. Challouf, N. Souissi, M. Ben Messaouda,
electrochemical exploration of the Juglans R. Abidi, and A. Madani, “Origanum
regia green fruit shell extract as a sustainable majorana: Extracts as Mild Steel Corrosion
and highly efficient green corrosion inhibitor Green Inhibitors in Aqueous Chloride
for mild steel in 3.5 wt% NaCl solution,” J. Medium,” J. Environ. Prot. (Irvine,. Calif).,
Mol. Liq., vol. 284, pp. 682–699, 2019. vol. 07, no. 04, pp. 532–544, 2016.
[2] Z. Sanaei, T. Shahrabi, and B. [12] P. Dhaundiyal, S. Bashir, V. Sharma, and A.
Ramezanzadeh, “Synthesis and Kuma, “An investigation on mitigation of
characterization of an effective green corrosion of mildsteel by origanum vulgare
corrosion inhibitive hybrid pigment based on in acidic medium,” Chem. Soc. Ethiop.
zinc acetate-Cichorium intybus L leaves Authors, vol. 33, no. 1, pp. 159–168, 2019.
extract (ZnA-CIL.L): Electrochemical [13] F. Fadel et al., “Antifungal activity and anti-
investigations on the synergistic corrosion corrosion inhibition of origanum compactum
inhibition of mild steel in aqueous,” Dye. extracts,” Int. J. Electrochem. Sci., vol. 8,
Pigment., vol. 139, pp. 218–232, 2017. no. 9, pp. 11019–11032, 2013.
[3] E. kamali Ardakani, E. Kowsari, and A. [14] I. Lukovits, E. Kálmán, and F. Zucchi,
Ehsani, “Imidazolium-derived polymeric “Corrosion inhibitors - Correlation between
ionic liquid as a green inhibitor for corrosion electronic structure and efficiency,”
inhibition of mild steel in 1.0 M HCl: Corrosion, vol. 57, no. 1, pp. 3–8, 2001.
Experimental and computational study,” [15] S. Limited., “Índice de corrosión,” Oilfield
Colloids Surfaces A Physicochem. Eng. Asp., Glossary en Español, 2019. [Online].
2019. Available:
[4] W. Francisco Martín, S. Gil Fundora, and B. https://www.glossary.oilfield.slb.com/es/Ter
Treto Monzón, “Deterioro de los ms/c/corrosion_rate.aspx. [Accessed: 26-
materiales,” in Fundamentos de la Nov-2019].
Corrosión y protección de materiales, 2014,
pp. 4–5. 7. ANNEXES
[5] S. A. Umoren, M. M. Solomon, I. B. Obot,
and R. K. Suleiman, “A critical review on Sample concentrations 1 to 6 were calculated as
the recent studies on plant biomaterials as follows:
corrosion inhibitors for industrial metals,” J.
Ind. Eng. Chem., vol. 76, pp. 91–115, 2019.
[6] R. Pierre R., “Principles of Electrochemistry
Applied to Corrosion,” Mater. Perform., vol.
80, no. March, p. 80, 2007. Where the initial concentration
[7] R. Pierre R., “Corrosion and the
Environment,” Mater. Perform., vol.
January, p. 80, 2007.
[8] N. Asrar et al., “Corrosion: the most The following tables show the values of the
extensive fight,” Oilf. Rev., vol. 28, no. 2,
concentrations calculated according to the
pp. 36–51, 2016.
[9] A. Dehghani, G. Bahlakeha, B. aforementioned equation
Ramezanzadehb, and M. Ramezanzadehb,
HCl
“Electronic/atomic level fundamental Inhibitor Total Inhibitor
Sample Volume
theoretical evaluations combined with Volume Volume Concentration
0.513M
electrochemical surface examinations of
1 0 50 50 0
Tamarindus indiaca aqueous extract as a new
3 10 50 60 250.46
green inhibitor for mild steel in acidic
5 20 50 70 429.37
solution (HCl 1 M),” J. Taiwan Inst. Chem.
Eng., vol. 102, pp. 349–377, 2019.
[10] R. Pierre R., “Corrosion Inhibitors,” Mater.
Perform., vol. December, p. 96, 2007.
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 Inhibitor
HCl
Total Inhibitor And the total area of cm2 to in2 is equal to:
Sample Volume
Volume Volume Concentration
0.513M
2 0 50 50 0
4 10 50 60 250.46 The following table shows the values of the areas
6 20 50 70 429.37 calculated according to the aforementioned
equations
A cylindrical sample of mild steel was used to Sample Heigh: h Area cm2 Area in2
calculate the density of the metal, knowing the 1 0.4 10.3672 1.6069
following: 2 0.5 11.0584 1.714
Density: 3 0.25 9.3305 1.4462
4 0.45 10.7128 1.6604
5 0.35 10.0217 1.5533
6 0.4 10.3672 1.6069

Where mass m was calculated with an analytical For the calculation of efficiency the following
balance resulting in: calculation was made:

And volume V was calculated as

Corrosion rate = ∆w/A.t

Where:

∆w = Metal weight loss

Where d and h are the diameter and height of the
cylinder respectively, which were measured with a
A = Surface area studied
Vernier ruler:
t = Metal exposure time

Then, the density is:

On the other hand, since the 6 cylindrical samples

had different heights, the total area calculation was
calculated by the following formula:

Where d is the diameter and h is the height of the

cylinder

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