sustainability

Article
Investigation of Eggshell Agro-Industrial Waste as a Potential
Corrosion Inhibitor for Mild Steel in Oil and Gas Industry
Omotayo Sanni *, Samuel Ayodele Iwarere and Michael Olawale Daramola *

Department of Chemical Engineering, University of Pretoria, Lynnwood Road,

Hatfield, Pretoria 0028, South Africa; [email protected]
* Correspondence: [email protected] (O.S.); [email protected] (M.O.D.)

Abstract: Corrosion inhibitors are generally used in reducing metallic corrosive effects. Nevertheless,
most inhibitory compounds have harmful effects on the environment, as well as being expensive
and toxic. Therefore, there is growing awareness of the need to replace petroleum inhibitors with
eco-friendly inhibitors. Eggshell agro-industrial waste (ESAW) is a compound with high inhibitive
activity and its utilization is desirable to minimize the quantity of agricultural waste generated.
Hence, this study aims to demonstrate the inhibition efficiency of eggshell extract, a waste compound,
on mild steel (material frequently utilized in the oil and gas sector) in one molar hydrochloric acid
solution accessed via weight loss and electrochemical methods. Potentiodynamic polarization results
shows that the current densities of mild steel corrosion significantly decreased using eggshell agro-
industrial waste. Similarly, electrochemical impedance spectroscopy results suggest that eggshell
agro-industrial waste enhances the mild steel polarization resistance significantly. The inhibitor
performance increases with increasing eggshell agro-industrial waste concentration, with optimum
efficiency of 97.17%. The inhibition was due to the adsorption and adhesion of the eggshell agro-
industrial waste constituents on the surface of the mild steel; the adsorption obeys the Langmuir
adsorption isotherm model. Compared with various reported corrosion inhibitors in the literature,
eggshell agro-industrial waste is very effective. Therefore, eggshell agro-industrial waste can be
recommended as a potential inhibitor in the oil and gas sector.

Keywords: oil and gas industry; mild steel; corrosion; sustainable inhibitors; agro-waste
Citation: Sanni, O.; Iwarere, S.A.;
Daramola, M.O. Investigation of
Eggshell Agro-Industrial Waste as a
Potential Corrosion Inhibitor for Mild
1. Introduction
Steel in Oil and Gas Industry.
Sustainability 2023, 15, 6155. Mild steel has been extensively utilized for numerous years in the oil and gas sector
https://doi.org/10.3390/su15076155 owing to its low cost and outstanding mechanical properties. However, in this industry,
the materials are susceptible to localized and general corrosion on exposure to aggressive
Academic Editor: Agostina Chiavola
media [1]. Nevertheless, mild steel is prone to corrosion process, mostly in acid environ-
Received: 17 February 2023 ments [2,3]. Several acids, such as acetic, hydrochloric, and hydrofluoric acid, are typically
Revised: 13 March 2023 utilized for descaling, pickling, industrial acid cleaning, and oil well acidizing in the in-
Accepted: 30 March 2023 dustry. The costs owing to corrosion in oil refining plants and natural gas sweetening is
Published: 3 April 2023 estimated to be 25% of the total maintenance budget [4]. Corrosion inhibitor is added to the
electrolytic solution to reduce the corrosion effects in acidic environments. One of the most
practical means of mitigating the corrosion process and extending mild steel’s useful life is
the use of organic inhibitors—that is, substances that are directly applied to the corrosive
Copyright: © 2023 by the authors.
solutions and interact with the material surface, thus forming defensive layers. Generally,
Licensee MDPI, Basel, Switzerland.
the challenges of corrosion mitigation are that the reagents or synthesis methods used are
This article is an open access article
hazardous to the environment and/or human health and very expensive. As a result, in the
distributed under the terms and
last few years researchers have investigated feasible alternative green options with good
conditions of the Creative Commons
Attribution (CC BY) license (https://
corrosion inhibition efficiency that are also safe for the ecosystem [5–9].
creativecommons.org/licenses/by/
Corrosion inhibitor is generally utilized to decrease the aggressive attack on mixing
4.0/). tanks, coil tubing, well tubular, and other metal surface in acid media. The application

Sustainability 2023, 15, 6155. https://doi.org/10.3390/su15076155 https://www.mdpi.com/journal/sustainability

Sustainability 2023, 15, 6155 2 of 20

of inhibitor is one of the most practical techniques (typically performed in acid environ-
ments) where prevention of metallic dissolution and acid consumption is crucial. The use
of corrosion inhibitor is a cost-effective and realistic means of protecting metal against
corrosion in the oil and gas sector. Indeed, the largest consumer of corrosion inhibitors
is the petroleum industry [10,11]. It should be pointed out that replacing this material
with a high-grade corrosion-resistant alloy could be costly compared to the application
of inhibitors. In the last few years, several acids, such as arsenic or arsenate acid, and
inorganic salts were utilized as inhibitors; these compounds have been substituted by
organic inhibitors as they are environmentally friendly with higher efficiency. Therefore,
substituting this toxic compound with biodegradable and ecological alternatives is now of
great interest. The technological use of food and agro-industrial waste has been studied
extensively to reduce waste disposal and increase the agro-industry’s value. Different
organic inhibitors are available in controlling the steel corrosion in acidic environments.
Most effective organic inhibitors have been reported to contain aromatic character that
facilitates the inhibitor adsorption on the metal surface and/or heteroatoms (nitrogen, oxy-
gen, and sulfur) [12,13]. The physicochemical properties, such as the inhibitor’s electronic
structure, π-orbital character, and electron densities at the donor atoms, play significant
roles in the inhibitors adsorption propensity on the surface of the metals. Interestingly,
many agricultural waste products contain substances that can serve as effectual corrosion
inhibitors. Waste management is one of the most complex concerns worldwide [14–16].
It is expected that waste is properly disposed without pollution danger. To achieve this
aim, the European Environment Agency has suggested that appropriate guidelines should
be given to policymakers and the public on waste management [17]. In the US alone, the
Associated Press Report (2008) estimated that about 115 million kg (250 million pounds)
of waste is generated annually. An increase in food waste generation is expected since
increasing food consumption is an emerging trend. Therefore, the utilization of agricultural
wastes as inhibitors in the petroleum industry could have economic benefits and offer more
green approach for creating a sustainable environment.
The inhibition tendencies of different agricultural waste types have been examined [18–24].
Shahmoradi et al. [19] investigated the corrosion inhibition behavior of pistachio shell on
steel in hydrochloric acid solution and the adsorption that was owing to the adsorbed
molecular species on the metal surface. Shahmoradi et al. [20] investigated the inhibiting
performance of walnut fruit containing aromatic rings on mild steel in acid solution. Pal
and Das [24] examined the effect of tea solid waste in HCl solution on mild steel corrosion
and reported its physisorption inhibition mechanism. The authors clarified that tea solid
waste influences the kinetics of hydrogen evolution. Odewunm et al. [21] investigated the
inhibition performance of water melon extract on mild steel in H2 SO4 and HCl solutions.
The authors found that water melon is an effective inhibitor. Kaban et al. [23] examined
the effects of rice husk in acid solution. They proposed that rice husk is a good inhibitor
and the adsorption occurs through heterocyclic and aromatic rings. Mohammed et al. [25]
studied date palm seed’s inhibition propensity on steel in HCl solution. The authors
reported that date palm seed inhibition takes place through the adsorption mechanism.
Globally, agro-industrial activity generates huge waste. Most of the generated waste is
utilized as animal feed [26]. This waste contains huge amount of antioxidant compounds
and nutrients, which can be utilized in obtaining substances with inhibitory tendencies,
improving the agro-industrial waste economy, and adding value to the waste. Many tons
of eggshell waste is been generated per annum; its composition includes high content of
natural antioxidants. In addition, it is rich in calcium, protein, and other minerals, and is
incorporated into many diets and food products [27]. However, there is no literature on
the performance of ESAW for mild steel in a 1 M hydrochloric acid solution. Hence, this
research aims to examine the application of eggshell from agricultural waste as inhibitors in
HCl solution. Consideration of agricultural waste (eggshells) for application as a corrosion
inhibitor is of interest owing to fact that consumption of egg is increasing. Such increases
in its consumption will inevitably lead to increases in its disposal. Exploring the idea of
Sustainability 2023, 15, 6155 3 of 20

proposing waste management, with economic value, coupled with the search for sustainable
inhibitors, the eggshell used in this research was generated in South Africa. Therefore, the
objective of this research is to investigate the potential of eggshell extract as a corrosion
inhibitor that will proffer a solution to corrosion deterioration of mild steel used in the oil
and gas industry. Using eggshells as corrosion inhibitor tends to minimize the amount of
waste generated.

2. Experimental Section
2.1. Materials and Methods
1 M hydrochloric acid was used as the corrosive solution in this experiment was
prepared from 37% purity concentrated HCl (Sigma Aldrich, St. Louis, MO, USA) and
was used without further purification. The stock ESAW inhibitor (100, 200, 300, 400,
and 500 ppm) solution was prepared by diluting 1 M HCl solution with double-distilled
water and then diluted to the concentration of hydrochloric acid suitable for pickling and
descaling mild steel. Table 1 shows the material composition used in this study. The
experiments were conducted in aerated stagnant solution and reproduced three times in
similar conditions to ensure reproducibility at a temperature of 302 K.

Table 1. The mild steel composition.

Element Si P S Mn Al C Fe
Composition, weight % 0.38 0.09 0.05 0.05 0.01 0.21 Balance

2.2. Electrochemical Measurements

Electrochemical and gravimetric tests were performed to evaluate ESAW’s anticor-
rosive properties. Specifically, electrochemical methods, including linear polarization
resistance, potentiodynamic polarization, and electrochemical impedance spectroscopy,
were utilized to assess the inhibition performance of ESAW. A potentiostat and frequency
response analyzer driven by NOVA 2.1 software were used for the electrochemical corrosion
tests. The test was conducted in an Autolab Potentiostat/Galvanostat (Metrohm, Utrecht,
The Netherlands) with three-electrode cells: mild steel sample as working electrodes,
platinum rod as counter electrodes, and silver/silver-chloride (Ag/AgCl) as reference
electrodes. The three-electrode flat cell electrochemical compartment was designed with
a 1 cm2 surface area of mild steel exposed to the aggressive media. The specimens were
ground with different grades of emery papers (400, 600, 800, 1000, and 1200 grits), polished,
and washed; the electrochemical tests were then conducted. The NOVA 2.1.5 software
was utilized to estimate the electrochemical data. The impedance measurement (EIS) was
recorded at 10 mV amplitude. The EIS result was modeled using ZSimpWin 3.20 software.
The potentiodynamic polarization experiment was conducted at 0.5 mV/s scan rate before
the electrochemical experiment; the specimen was dipped in the solution for two hour to
attain free corrosion potential. The impedance measurement was calculated by using the
inductance resistance (RL), charge transfer resistance (Rct), and film resistance (Rfm) to
estimate the total impedance resistance. Equations (1)–(3) were utilized to calculate the
inhibition efficiencies (IE) [28]:

Rpinhibitor − Rpblank
IE = × 100 (1)
Rpinhibitor

Rctinhibitor − Rctblank
IE = × 100 (2)
Rctinhibitor

icorrblank − icorrinhibitor
IE = × 100 (3)
icorrblank
Sustainability 2023, 15, 6155 4 of 20

where Icorr is the corrosion current density (from LPR study), Rct is the charge transfer
resistance (from EIS study), and Rp is the polarization resistance (from PP study).

2.3. Weight Loss Tests

The weight loss was carried out in agreement with the ASTM G1-03 (American Society
for Testing Material, West Conshohocken, PA, USA). Weight loss tests were conducted to
establish the long-term inhibitive performance of ESAW on mild steel in addition to the
electrochemical tests. The corrosion inhibitor test should be at least 100 h for practical
application of inhibitor in the petroleum industry [29]; therefore, in this research the weight
loss assessment was carried out in a 250 mL corrosive solution in the absence and presence
of diverse ESAW concentrations for 336 h. The cleaning of the samples was the same to the
electrochemical corrosion test specimens. A digital balance was used to measure the weight
loss before and after the corrosion test. The test was performed three times to confirm
reproducibility. The sample was cut with a drilled hole (2 mm drilling beat) at the center
of the specimen to enable the coupon suspension in the corrosive media. The specimen
was ground with emery papers (400 to 1200), polished, and cleaned prior to the weight loss
tests. The specimen dimension was 3.00 cm × 2.92 cm × 0.50 cm after being abraded with
silicon carbide of different sizes. We freed the coupons of polished residue and moisture by
following these steps: rinsing and cleaning the coupons with acetone and ethanol, drying
them in air, and then storing them in the desiccators before use. The corrosion product was
mechanically and chemically loosened following the ASTM cleaning standard procedure;
this occurred after the complete immersion of the samples every 24 h. Equation (4) was
used to calculate the corrosion rate, while the efficiency was estimated by Equation (5) [30]:

87.6 W
Corrosion rate = (4)
density( g/cm3 ) xarea(cm2 ) xtime(hours)

Corrosionrateblank − Corrosionrateinhibitor
Inhibition e f f iciency = (5)
Corrosionrateinhibitor
where W is the difference between the initial and final weight of the mild steel immersed in
the HCl media.

2.4. Surface Characterization

The coupons immersed in 1 M HCl media in the presence and absence of ESAW were
investigated via scanning electron microscopy to examine the morphology of corrosion
attack, and by energy-dispersive X-ray spectroscopy to determine elemental composi-
tion (EDX).

3. Results and Discussion

3.1. Characterization of the Egg-Shell Agro-Industrial Waste
The ESAW morphology shown in Figure 1 is characteristically alveolar and fibrous,
with the irregular rod resulting from the milling process. Figure 2 shows the EDX mapping.
It is observed in Figure 2 and Table 2 that the ESAW presents intensities of calcium,
oxygen, and carbon. The proportion of these constituents is 37.3%, 35.7%, and 25.0%,
respectively. High carbon quantities are present in the ESAW as shown in Figure 2. From
the data given in Figures 1 and 2, the main constituents in the eggshell are shown to be
O, C, Ca, K, and Cl—which are all organic compound features—and S, Mg, Na, P, and
Si. The O and C present in the eggshell compound are potential sources of electron pairs
available for adsorption on the surface of the metal; this supports the inhibition of corrosion
in the acid solution and consequent partial blockage of the metal [31]. The eggshell has a
high level of protein, which in turn presents O, and C atoms; therefore, this compound
can be proposed for use as an inhibitor. The extraction of the rich constituents present
in the eggshell could be achieved by diverse means before being utilized as inhibitors in
other aggressive media/metal. The molecular structure of ESAW (Figure 3) was confirmed
Sustainability 2023, 15, 6155 5 of 20

by O-H, and C-O groups, indicating that the ESAW has functional groups containing
heteroatoms. This functional group is capable of aiding the inhibitor’s adsorption on the
metal. FTIR test of the ESAW was conducted to affirm the existence of heteroatoms that
have different aromatic systems and functional groups. FTIR test of the ESAW (Figure 4)
was conducted in the range of 400–5000 cm−1 .

Figure 1. SEM image of the eggshell agro-industrial waste (500× zoom).

Figure 2. EDX mapping of eggshell agro-industrial waste.

Sustainability 2023, 15, 6155 6 of 20

Table 2. Elemental analysis of the eggshell agro-industrial waste.

Element Eggshell (Wt %)

C 37.3
O 35.7
Ca 25.0
K 0.8
Cl 0.4
S 0.3
Mg 0.3
Na 0.2
P 0.1
Si 0.1

Figure 3. Molecular structure of the eggshell agro-industrial waste.

Figure 4. FTIR spectroscopy of the eggshell agro-industrial waste.

Sustainability 2023, 15, 6155 7 of 20

3.2. Corrosion Inhibition Evaluation

3.2.1. Electrochemical Impedance Spectroscopy (EIS) Analysis
Shown in Figure 5 is the Nyquist plot in the acidic electrolyte with and without
ESAW. Figure 6 represents the equivalent circuit model used in this study, and Figure 7
shows the Bode plots in the acidic electrolyte with and without ESAW. The phase angle,
Nyquist impedance spectra, and Bode’s modulus were obtained to examine the ESAW
capacitive behavior of mild steel and the 1 M HCl solutions interface in the presence
and absence of different inhibitor concentrations. As presented in Figure 6, the basic
equivalent circuits model was utilized for the uninhibited mild steel in the electrolyte,
which consists of Rs (solution resistance), CPE (constant phase element), and Rct (charge
transfer resistance). However, with ESAW, Cf (film capacitance) and Rf (film resistance,
formed due to the material passivation layer) was included in the basic equivalent circuit.
CPE is defined by n and Y0 and was used instead of a pure capacitance due to itsnon-
homogenous metallic surface.

Figure 5. (a,b) Mild steel Nyquist plots obtained in the presence and absence of the eggshell agro-
industrial waste for Rp with diverse eggshell agro-industrial waste concentrations (0, 100, 200, 300,
400, and 500 ppm).
 500 400 300 200 100 0
Inhibitor concentration (ppm)

Sustainability 2023, 15, 6155 Figure 5. (a,b) Mild steel Nyquist plots obtained in the presence and absence of the eggshell8 of 20
agro-industrial waste for Rp with diverse eggshell agro-industrial waste concentrations (0, 100, 200,
300, 400, and 500 ppm).

Figure 6. Equivalent circuits (a) blank and (b) with Eggshell agro-industrial waste used to fit EIS
Figure 6. Equivalent circuits (a) blank and (b) with Eggshell agro-industrial waste used to fit EIS
data. (CPE: constant phase
data. (CPE: element;
constant Rct: charge
phase element; transfer
Rct: charge resistance;
transfer resistance; Cf: filmcapacitance;
Cf: film capacitance; Rf: film
Rf: film
resistance). resistance).

Figure 7. Bode phase (a) and Bode modulus (b) in the absence (blank) and presence of the eggshell
agro-industrial waste (100 to 500 ppm).
Sustainability 2023, 15, 6155 9 of 20

The mild steel Rp (polarization resistance) was estimated by adding Rf and Rct val-
ues [32]. The metal shows an Rp value of 87.18 Ω cm2 in the uninhibited solution. The
presence of 100 ppm ESAW in the solution increased the polarization value. A further raise
in the ESAW dosage increased the metal Rp:Rp = 8718 (200 ppm); 9510 (300 ppm); 1041
(400 ppm); 1055 Ω cm2 (500 ppm). The obtained results show that as the concentration of
ESAW increases, the Rct value also increases, showing that the ESAW is adsorbed success-
fully on the metal as the Cdl values drop. The Cdl drop could be related to a decrease in the
dielectric constant surrounding, denoting the possibly that ESAW performs via adsorption
at the interface region. This could also be ascribed to the relaxation of intermediate ad-
sorbed elements such as the H+ ads with negative potentials due to the interface coverage
for H+ ads adsorbed [33]. This decline in Cdl can possibly be ascribed to the inhibitor
molecules limiting the charged species’ access to the mild steel surface. The observed trend
can be ascribed to the ESAW adsorbed onto the metal, promoting corrosion inhibition. A
similar trend was reported by Odewunmi et al. [34]. When Barley is used as an inhibitor in
1.5 mol L−1 H2 SO4 , a similar trend was also recorded [35]. The ESAW present increased
the Rct of the metal; the eggshell can also be utilized as a replacement for synthetic organic
compounds for protecting mild steel against corrosion. The high frequency section of the
Nyquist plots and polarization resistance (Figure 5a,b) was observed to display capacitive
loops with increased depressed semi-circle diameters and Bode’s modulus impedances
(Figure 7a,b); these increases were proportional to the ESAW concentrations in the acidic so-
lution. This observation can be ascribed to the formation of protective films that obstructed
the process of corrosion by displacing the corroding ions on the mild steel surface [36].

3.2.2. The Potentio-Dynamic Polarization

The polarization curve was obtained to improve understanding of the adsorption that
takes place with the ESAW in the aggressive solutions and to qualitatively interpret its
occurrence at the cathodic and anodic sites. The mild steel potentio-dynamic polarization
plot in the electrolyte without/with ESAW is shown in Figure 8; the equivalent data is
shown in Table 3. Table 3 shows high Rp values as the ESAW concentrations increase
in the aggressive media. Moreover, the polarization resistance value was similar to the
Rct value, verifying the anticorrosive efficiency of ESAW as a promising inhibitor. The
graph illustrates that the inhibited solutions show lower reduction and oxidation values in
current density, denoting that ESAW affects both hydrogen evolution (cathodic process)
and iron dissolution (anodic process). The declined corrosion current observed is more
prominent as the ESAW concentrations increase in the aggressive solution, supporting the
previous results; the polarization curve shape is not altered, denoting that ESAW does not
affect the corrosion mechanism [37]. The current density of the uninhibited solution was
0.00646 A/cm2 ; this figure was significantly reduced to 3.761 × 10−5 A/cm2 with 100 ppm
of ESAW. An increase in the ESAW concentrations (100–500 ppm) denotes a marginal bene-
fit in terms of resistance to corrosion, with current density values of: 3.761 × 10−5 A/cm2
(100 ppm), 2.670 × 10−5 A/cm2 (200 ppm), 2.150 × 10−5 A/cm2 (300 ppm),
2.290 × 10−7 A/cm2 (400 ppm), and 2.150 × 10−7 A/cm2 (500 ppm). The corrosion rates
estimated for mild steel from the Icorr measured by the Tafel measurements were 2.421,
1.222, 0.671, 0.537, 0.022, and 0.009 mm/year, respectively, with and without the different
concentrations of ESAW presented in Table 3. This performance denotes the concentration
dependence of ESAW on the mild steel surface in 1M HCl solutions. Addition of ESAW to
the acid solution shifted the metal Ecorr in a negative direction. This observation could be
ascribed to the reduced cathodic kinetics reaction with the ESAW. As a result, the anodic
polarization curve exhibited breakdown and passivity potential for the inhibited mild
steel sample; this phenomenon was not observed in the uninhibited sample. The potential
breakdown can, however, be ascribed to the high chloride ions and polarization voltage
present in the corrosive solution, which causes passivity breakdown. The Ecorr shift was in
the range of ±85; therefore, the mixed-type nature of ESAW can be affirmed for mild steel
Sustainability 2023, 15, 6155 10 of 20

in the HCl solution [38]. The LPR observed trend is in agreement with the electrochemical
measurements (EIS).

Figure 8. Tafel polarization curves of mild steel with different concentrations of the eggshell agro-
industrial waste.

Table 3. Electrochemical parameters obtained by potentio-dynamic polarization for mild steel in 1 M

HCl solution in the absence and presence of the eggshell agro-industrial waste.

Inhibitor Polarization
Ecorr Icorr Corrosion Rate
Concentration Resistance
(V) (A/cm2 ) (mm/Year)
(ppm) (Ω)
0 −0.320 0.00646 39 2.421
100 −0.363 3.761 × 10−5 108 1.222
200 −0.395 2.670 × 10−5 114 0.671
300 −0.385 2.150 × 10−5 339 0.537
400 −0.513 2.290 × 10−7 899 0.022
500 −0.519 2.150 × 10−7 1031 0.009

3.2.3. Weight Loss Measurements

The weight loss technique of examining the inhibition performance is useful due to
its reliability and simplicity of application. Figure 9 presents the weight loss results for
mild steel in 1 M HCl solution with/without ESAW exposed for 336 h. Without ESAW,
the corrosion rate after 24 h was 0.83784 mm/year and increased to 0.60979 mm/year
after 336 h. With 100 ppm ESAW, the weight loss value was 0.42477 mm/year and 0.16821
mm/year after 24 and 336 h, respectively. The effectiveness of the ESAW on mild steel
in 1MHCl solution was apparent in Figure 9 as the inhibitor’s effectiveness increased
with increased ESAW concentration. The inhibitor’s percentage efficiency rates of 62.75,
70.12, 76.31, 91.50, and 97.17 were achieved at 100, 200, 300, 400, and 500 ppm ESAW,
respectively. This denotes that more molecule interacted with the surface of the metal and
formed the protective film that delays the process of corrosion [39]. However, an increase
in the exposure time displayed notable discrepancies in the ESAW performance at diverse
concentrations, as presented in Figure 9a,b. The investigated compound shows satisfactory
Sustainability 2023, 15, 6155 11 of 20

efficiency even at low concentrations, lowering the corrosion rate value. In weight loss
tests, the inhibitor’s performance is directly proportional to the metal surface’s protection
from contact with the corrosive media; thus, the degree of surface coverage indicates that
with an increase in ESAW concentrations, there are better organic molecules available to
interact with the mild steel surface, thereby forming protective films and protecting the
surface of the metal [32]. Higher ESAW concentrations promote higher surface blocking,
thereby leading to increase in the inhibitor’s efficiency. The presence of the ESAW reduces
the corrosion rate and, as a result, boosts inhibition efficiency; this behavior was enhanced
by increasing the inhibitor dosage. It is obvious that as the inhibitor concentration rises, the
inhibition efficiency increased to 97.17% at 500 ppm, demonstrating that the presence of
this compound reduced iron dissolving in 1 M HCl solution and implying that it functions
as an inhibitor. In both blank and inhibited solutions, the relationship between corrosion
rate and exposure time is linear. In this situation, the ESAW is adsorbed on the metal and
prevents corrosion by either changing the mechanism of the anodic and cathodic partial
processes or blocking the reaction sites (anodic and cathodic) [40]. When compared to
the efficiency obtained in prior works [18–25], the maximal inhibitor efficiency obtained
utilizing 500 ppm of eggshell is higher (97.17%). This result can be linked to high organic
molecules being adsorbed on the mild steel surface, signifying excellent surface protection
due to the extensive compact films formed. This result could be due to the presence of
functional groups in addition to the aromatic substituted benzene ring, which is an electron
donating group. The investigated eggshell showed an optimum efficiency greater than 96%,
denoting that agricultural waste can replace synthetic organic compounds as inhibitors in
the oil and gas industry. The obtained result from the weight loss test is in good agreement
with electrochemical tests.

Figure 9. Cont.
Sustainability 2023, 15, 6155 12 of 20

Figure 9. Corrosion rate (a) and inhibitory efficiency (b) as a function of exposure time in the absence
(blank) and presence of the eggshell agro-industrial waste (100 to 500 ppm).

3.3. Adsorption Mechanism

Generally, it is established that corrosion inhibitors form a barrier or protective film
on the metal surface, thereby reducing the corrosion rate of the metal. The process of
adsorption in an aqueous solution can be considered as a substitution process between the
water molecules at the electrode surface [H2 O(ads)] and organic compounds in the aqueous
phase [Org(sol)] [35]:

Org(sol ) + xH2 O( ads) → Org( ads) + xH2 O(sol ) (6)

where x is the number of water molecules substituted by one organic inhibitor. The interface
between the metal surface and the inhibitor could be explained by adsorption isotherm.
The surface covered fraction (θ) by molecules adsorbed is directly proportional to the
inhibitors performance. Therefore, higher inhibitor surface coverage is significant for
excellent corrosion protection. The inhibitors’ degree of surface coverage was calculated
following the method of Matos et al. [35]. The adsorption isotherm model is generally used
to understand the inhibition mechanisms. The isotherm adsorption models commonly used
for corrosion inhibitors are: Langmuir, Tempkin, Freundlich, Flory-Huggins, and Frumkin.
The surface coverage values were calculated using weight loss data in the presence of
various inhibitor concentrations, and numerous adsorption isotherms were used to find the
best fit from the data. Figure 9 shows a straight line shape as the graphic representation of
C/θ against C; this approach is known for describing a monolayer assumption model which
predicts the Langmuir adsorption isotherm where the inhibitor molecule interacts with the
surface of the metal [41]. With Langmuir’s mathematical equation, it is possible to estimate
the Kads value through the linear coefficient shown in Figure 10. The high Kads value is
similar to the values reported in the literature [42], indicating that the system is improved
by the organic molecules adsorbed on the metal surface. This study proposes that ESAW is
an excellent inhibitor for mild steel in acid environments. Even at low ESAW concentration,
mild steel corrosion significantly decreases and the inhibitor efficiency increases with
increased ESAW concentration. The comparison of different reported corrosion inhibitors
in similar conditions with the same degree of protection of ESAW is given in Table 3. It is
Sustainability 2023, 15, 6155 13 of 20

obvious that ESAW is highly effective, which can be ascribed to its exclusive structure that
contains aromatic rings, nitrogen, and sulfur; thus, it could serve as an efficient corrosion
inhibitor. Hence, ESAW can be regarded as a potential inhibitor for use in the oil and
gas industry.

Figure 10. Langmuir adsorption isotherm of the eggshell agro-industrial waste.

3.4. Economic Considerations and Comparative Study of the Eggshell Extract

The use of corrosion inhibitors is considered as one of the most economical and
effective means of protecting metals from corroding. Integrated valorization of waste
is a progressive form of resource conservation due to its environmental and economic
values. In almost every country in the world, the extraction of organic compounds from
food waste has become a significant concern in the field of waste management. Searching
for cost-effective, efficient, and environmentally friendly metal corrosion inhibitors in
aggressive media is a continuous process. In the present work, we tried to propose eggshell
extract as one of the inhibitors which satisfy the above-mentioned qualities. Eggshell
extract showed a high inhibition efficiency of 97.17% in 1 M HCl solution; to confirm the
inhibition performance of eggshell extract, its efficiency was compared with the results
of other authors (Table 4). As can be seen in Table 4, the eggshell extract presented great
inhibition efficiency on mild steel corrosion in 1M HCl solution. In contrast, inhibitorssuch
as Ceratonia siliqua leaves’ seed oil show higher inhibition but are not suitable for mass
steel production due to their higher cost. Therefore, it is necessary to study the techno-
economic aspect of using eggshell extract. The eggshell was collected at 0$ per kg. The
total price of the eggshell extraction process, including the cost of water and ethanol, was
less than 1$ per kg.
To achieve high inhibition efficiency, other inhibitors reported in Table 5 were added
in higher amounts, while only 500 ppm of the eggshell extract was used for the present
study. This makes eggshell extract a cost-effective alternative to other inhibitors reported in
Tables 4 and 5. While most of the green inhibitor extraction required a high amount per kg, a
spend of less than 1 $ was sufficient to develop 1 kg of eggshell extract, which is considerably
less than the costs required for any of the inhibitors reported in Table 5. This makes eggshell
extract a suitable inhibitor for large-scale production and industrial applications.
Sustainability 2023, 15, 6155 14 of 20

Table 4. Comparing the efficiency of eggshell agro-industrial waste against other inhibitors in similar
conditions.

Compound Average Efficiency Reference

Pistachio shell 92% [19]
Walnut fruits 95% [20]
Tea solid waste 90% [24]
Water melon 81.15% [21]
Rice husk 97.73% [23]
Date palm seed 95% [25]
Licuri 91% [28]
Barley waste 97% [35]
Ircinastrobilina 82% [43]
Spirogyra 88% [44]
Tinosporavordifolia 87.18% [45]
Wombolu extract 97.87% [46]
Cotton seed 95.7% [47]
Akebia trifoliate koiaz peels 90% [48]
Zea mays hairs waste 87.92% [49]
Pomegranate peels 96% [50]
Sugar beet pectin 93.9% [51]
Eggshell 97.17% This work

Table 5. Comparison cost of some green and commercial corrosion inhibitors in aggressive solution.

Maximum
Corrosion Inhibitor Cost perkgOfinhibitor, ($) Reference
Inhibitionefficiency (%)
Eggshell 97.17 Less than 1 Present study
Amorphophallus paeoniifolius
93 1–2 [52]
leaves extract
2-Mercaptobenzimidazole 53.0 85–110 [53]
N-[1-(benzotriazol-1yl)methl] ~ 85.0 3400–4000 [54]
Ginkgo leaf extract 92 200–300 [55]
Konjac glucomannan 93 180–200 [56]
Ceratonia siliqua L Seed Oil 98 300–400 [57]
Polysaccharide 96 500–1000 [58]

3.5. Surface Analysis

The surface morphology of the samples after 336 h of immersion to the electrolyte
without/with ESAW was conducted using scanning electron microscopy equipped with
energy-dispersive X-ray spectroscopy; the results are shown in Figure 11. The EDX results
are also shown in Figure 12 and Table 6 representing the elemental analysis of the eggshell
agro-industrial waste. The inhibited sample is smooth (Figure 11b) with small grooves
resulting from the metal preparation. It is obvious from the morphology that ESAW greatly
protected the mild steel surface from corroding. When the metal was immersed in the
1 MHCl solutions, the metal oxidation reactions occurred all over the metal surface, as
presented in Figure 11a, where the rough surface was observed. The uninhibited mild
steel sample was corroded severely, while with inhibited mild steel sample was smooth
with no noticeable sign of corrosion. The SEM image is connected to the weight loss result,
denoting that the inhibitor performs as excellent inhibitor for mild steel in HCl solution.
The comparison of Figure 11a,b denotes the effectiveness of the ESAW as a corrosion
inhibitor for mild steel in HCl solution. With the addition of 500 ppm ESAW, there is an
increase in the accessibility of the constituents’ element of the alloy. An adsorbed molecule
layer is formed, protecting the mild steel surface and leading to a less severe corrosion
process [59]; this result denotes that the organic molecule form a protective layer on the
surface of the mild steel. After 336 h in contact with HCl solution (Figure 12a), it is obvious
that the mild steel surface is attacked by the chloride ions. The oxygen atom detected by
Sustainability 2023, 15, 6155 15 of 20

the EDX analysis pointed to the corrosion products formed on the metal. The oxygen and
calcium percentages in Figure 12b are higher than the uninhibited sample, pointing to
the protective layer that ESAW substituents formed on the metal surface. Moreover, the
carbon substituent detected originated from the ESAW molecules in the presence of the
corrosion inhibitor.

Figure 11. SEM images of mild steel after immersion in HCl (a) without, (b) with 500 ppm of eggshell
agro-industrial waste.

Figure 12. EDX mapping of mild steel after immersion in HCl (a) without, (b) with 500 ppm eggshell
agro-industrial waste.

Table 6. Elemental analysis of the eggshell agro-industrial waste.

Element Blank With Inhibitor (500 ppm)

Fe 77.5 2.1
O 22.5 16.4
C - 63.9
N - 8.9
Cl - 3.1
Na - 1.9
K - 1.1
Sustainability 2023, 15, 6155 16 of 20

Table 6. Cont.

Element Blank With Inhibitor (500 ppm)

S - 1.0
Cr - 0.8
Ca - 0.4
Si - 0.1
Mg - 0.1
P - 0.1

3.6. Inhibition Mechanisms

Organic molecules act as corrosion inhibitors via adsorption on the surface of the
metal and form protective barriers. The phenomena that contribute to the barrier formation
are as follows:
• Interaction amid the protonated organic compound with anion on the metal through
cations from the compound oxidation process;
• Electrostatic attraction amid π-electron on the compound with vacant d orbital;
• π back interaction connecting the organic compound aromatic rings;
• A combination of the above.
Several organic corrosion inhibitors are heterocycles with unshared electron pairs on
the heteroatoms of inhibitor molecules (P, N, O, and S); the presence of polar functional
groups, such as Cl, OH, NO2 , CN, CH3 , CN, and others, along with double and triple
bonds, enables them to donate the electrons and hence easily become protonated in strong
corrosive electrolytic media such as HCl. Therefore, the inhibitor protects the outer layer of
the metal from the uninterrupted influence of the aggressive ions, preventing deterioration
of the metal. As a result, heteroatoms (Figure 3) are expected to play a significant role in
inhibitor compound adsorption on the metal surface; the functional groups (CH3 , OH)
are indicated in Figure 4. Since we are working with a complex molecule that forms
ESAW and acts as an excellent corrosion inhibitor, one of these phenomena was selected
to schematically represent what was discussed in the corrosion inhibition mechanism of
ESAW, as shown in Figure 13.

Figure 13. The proposed mechanism for the adsorption of eggshell agro-industrial waste on the
surface of mild steel in 1 M HCl solutions.
Sustainability 2023, 15, 6155 17 of 20

4. Conclusions
Preventing mild steel corrosion is important for the environment because corrosion is
a dreadful waste of money and natural resources. The eggshell is a sustainable alternative
to recover agro-industrial wastes from a sector known for producing tons of waste on
a daily basis. This process generates various products that can be used for a variety of
purposes. Hence, this research work aimed to use eggshell extract as a corrosion inhibitor
that will proffer solutions to corrosion deterioration of mild steel used in the oil and gas
industry. The effectiveness of ESAW as an inhibitor was investigated on mild steel in 1 M
HCl solutions via electrochemical and weight loss techniques, surface analysis by SEM,
and EDX, with the following outcomes:
• By raising ESAW inhibitor concentrations to 500 ppm, the corrosion inhibition effi-
ciency is increased to 97.17% as per the industrial application; this figure is compara-
tively better than that achieved in previous studies using tea solid waste, which had
an efficiency of 90%, and Pomegranate peels extract, which had an efficiency of 96%.
Consequently, the Fe+2 (ferrous ion) concentration is decreased in the corrosive solution;
• Electrochemical measurement shows that the presence of ESAW improves the mild
steel surface with a noticeable increase in Rct with the ESAW and desorption of an in-
termediate species. Potentio-dynamic polarization tests demonstrate the effectiveness
of ESAW, with an obvious decrease in the corrosion current densities. The tests show
that the ESAW behaves as a mixed-type inhibitor;
• The obtained results from PDP and EIS measurements were in good agreement and
both analyses are in favor of the increase in inhibition effectiveness of the ESAW with
increasing concentration;
• The inhibition was due to the adhesion or adsorption of ESAW constituent on the mild
steel surface without modifying the mechanism of corrosion; the adsorption follows
the Langmuir isotherm model;
• The outcomes of the analytical methods are in good agreement with (±2%), demon-
strating that the presence of ESAW inhibits mild steel corrosion in acidic conditions
and slows the process of iron dissolution in these situations. Ultimately, this study
proves that it is feasible to transform agro-industry wastes into sustainable inhibitors.
Hence, this study proposes that there is ample scope for the application of eggshell as
corrosion inhibitors in the oil and gas industry.

Author Contributions: O.S.: conceptualization; investigation; methodology; data curation; writing—

original draft preparation; writing—review and editing. S.A.I.: project administration; resources;
supervision. M.O.D.: project administration; validation; resources; supervision; funding acquisition.
All authors have read and agreed to the published version of the manuscript.
Funding: The authors appreciate the financial support of the Department of Chemical Engineering,
University of Pretoria, Pretoria, South Africa. Samuel A Iwarere is funded by the Government of the
United Kingdom through The Royal Society as a FLAIR Fellow [FLR\R1\201683].
Data Availability Statement: All data and material will be made available on request.
Conflicts of Interest: The authors declare no conflict of interest.

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