SPE-169637-MS

Application of Plant Extract for Inhibiting Corrosion in

Acidic Environments
Ravikant Belakshe, SPE; Lalit Salgaonkar, SPE, Halliburton
Copyright 2014, Society of Petroleum Engineers
This paper was prepared for presentation at the SPE International Oilfield Corrosion Conference and Exhibition held in Aberdeen, Scotland, UK, 1213 May 2014.
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
Use of chemical corrosion inhibitors is quite common in production and processing operations. Depending
on the type of acids used, different inhibitors have been developed to minimize corrosion and enhance the
life of metal tubulars. Development of new chemicals and chemistries, which maintain good protection of
materials under a variety of conditions while being environmentally acceptable, is an extremely chal-
lenging task.
This paper investigates the inhibitive properties of a new environmentally acceptable inhibitor toward
corrosion of different steel alloys in the presence of mineral and organic acids. The inhibitor explored in
this paper is a food grade chemical derived from a plant and commonly used in medicinal formulations.
It is easily available, non-polluting, and biodegradable, being of plant origin. The inhibitor composition
has several N, O, and S atoms containing alkaloid structures, which helps enhance the adsorption capacity
of the chemical as well as imparts corrosion inhibition properties. The inhibitor can be used either in the
form of a solid powder derived from the roots of the plant or in a liquid form derived by means of
extraction.
Corrosion inhibition of oilfield alloys, such as N-80, 13Cr-L80, and QT-800, were studied in the
presence of corrosive media, such as 7.5 and 15% HCl acid, and organic acid mixtures comprising acetic
and formic acid. Weight-loss measurements were used to evaluate the inhibition efficiency and a corrosion
loss of 0.05lb/ft
2
was considered as a pass. Tests were conducted on the metallurgies mentioned over
a temperature range of 150 to 275F.
The results disclosed illustrate the potential of the inhibitor to serve as an effective environmentally
acceptable inhibitor for the corrosion of steel alloys in the described temperature range. This single
inhibitor composition can be applied for both HCl and organic acid media in fresh water and salt brine
systems.
Introduction
Acidic fluids are present in many operations performed within the oil and gas industry. Several cases where
acidic fluids are often used in wells penetrating subterranean formations include both matrix stimulation and
fracture acidizing of carbonate formations, damage removal in sandstone formations, scale removal, pickling
of the tubings, and mud filter-cake cleanup. Acidic fluids can include one or more of a variety of acids, such
as hydrochloric, acetic, formic, hydrofluoric, or combinations of such acids. Use of these acids can cause
moderate to severe damage to the metal based downhole structures in the form of corrosion. Corrosion
tendencies and rates using mineral acids are generally higher and can increase substantially at elevated
temperatures. Corrosion rates using organic acids are usually relatively lower, but may not be negligible.
In general, corrosion is the loss of metal attributed to chemical or electrochemical reactions, which could
eventually destroy a structure. The corrosion rate will vary with time, depending on the particular conditions
to which a metal is exposed, such as the amount of water, pH, other chemicals, temperature, and pressure.
Corrosion of metals can occur anywhere they are presentwithin oil or gas production system, such as
in the downhole tubulars, equipment, and tools of a well, in surface lines and equipment, or transportation
pipelines and equipment. These tubulars, downhole equipment, and tools are primarily made up of carbon,
chrome, and stainless steels. Apart from Fe (iron), these alloys are also comprised of C, Si, Mn, S, P, Cr,
Ni, Cu, Zr, Mo, Co, and other trace elements, depending on their type. Iron exists in higher percentage
in all these alloys. Iron exists in a wide range of oxidation states, 2 to 8, although 2 and 3 are the
most common. Elemental iron is reactive to oxygen and water. Fresh iron surfaces appear lustrous
silvery-gray, but oxidize in normal air to give iron oxides, also known as rust. Unlike many other metals
that form passivating oxide layers, iron oxides occupy more volume than iron metal; thus iron oxides flake
off and expose fresh surfaces for corrosion. Also, iron has very low reduction potential compared to other
contents in an alloy; invariably, it is susceptible to more corrosion within the entire composition of an
alloy. Hence, protecting iron-containing alloys can be challenging (Craig and Anderson 1995).
Various corrosion inhibitors and intensifiers have been developed to minimize corrosion. Most
commonly used are organic corrosion inhibitors (e.g., quaternary ammonium salts, propargyl alcohol,
mannich base, hexamethylenetetramine, mercaptan-based), which are observed as very effective corrosion
inhibitors, though not considered environmentallyacceptable (Fink 2011).
Environmentally Acceptable Corrosion Inhibitors
There has been a growing realization in recent years to protect the environment from the effects of
hazardous chemicals. Thus, the use of environmentallyacceptable chemicals and additives has become
critical and serious efforts are being directed toward identifying safer chemistries. With due respect to
such requirements, , unsaturated aldehyde-based environmentally acceptable corrosion inhibitor
Cinnamaldehyde for HCl acid was proposed by Frenier and Growcock (1988) as a replacement for
hazardous arsenic and arsenic-compound-based corrosion inhibitors (Frenier and Growcock 1988).
Cinnamaldehyde is present in the spice called cinnamon used in sweet and savory foods. Recently
reported in literature, many plant-based environmentallyacceptable corrosion inhibitors are being devel-
oped and researched (Oguzie 2010; Choudhary et al. 2012). Oil and gas producing countries residing
within the North Sea (UK, Norway, Netherlands, and Denmark) and Australia have very stringent
environmental regulations related to the use of chemicals and additives (OSPAR 2014). Hence, inhibition
additives for acid usage require adherence to regulations, calling for continual improvement to environ-
mental characteristics while maintaining the performance. A consensus now appears to be emerging with
respect to the use of the term green chemicals (Gough 2000).
Because natural products or plant-based extracts are known to easily biodegrade, one approach toward
a more environmentally acceptable corrosion inhibitor is to evaluate plant-based natural products for
corrosion inhibition efficiency. This paper describes a plant extract derived from a naturally occurring
food grade chemical that is commonly used for medicinal purposes and demonstrates excellent corrosion
inhibition properties on oilfield carbon steel metal tubulars. These inhibition properties are exhibited both
in mineral acids (HCl) as well as organic acids (formic, acetic acids) at temperatures up to 275F. The
plant, WS, is a short shrub that grows in all dry and subtropical areas of India, South Africa, Congo, Egypt,
Morocco, Jordan, and Afghanistan. This naturally occurring plant product is ecofriendly, compatible,
nonpolluting, less toxic, easily available, biodegradable, and economic to be used as corrosion inhibitor.
2 SPE-169637-MS
Materials and Method
Materials
HCl acid (35% by wt) was used to make the acid blends by appropriate dilution with water. Two
different corrosion inhibitor intensifiers CII-1 and CII-2 respectively were used in this study. These
intensifier chemicals are known to synergistically enhance the action of the typical corrosion inhibitors.
A plant-based corrosion inhibitor was used in all of the tests. Because both solid powder of the plant
material and a liquid extract of the same were used during the course of this study. For ease of
understanding and the purpose of this paper, the solid plant-based inhibitor is represented as SCI and the
liquid extract is represented as LCI.
For preparing LCI, the roots of the plant were extracted twice with organic solvents and once with
water. This allowed collecting both the solvent soluble and aqueous soluble components in the extract.
These individual extracts were further concentrated by evaporating the solvent and water, respectively.
The thick slurries obtained after evaporation from these organic and aqueous parts were then mixed
together and dissolved in a small amount of water. A small amount of glycerol or sorbitol was added to
this mixture to help the contents dissolve or disperse in water.
Specimens of different alloys were used for corrosion testing. Table 1 presents the chemical compo-
sitions of alloys used.
Static High-Pressure/High-Temperature (HP/HT) Corrosion Weight-Loss
Test Procedure
Test coupons used during the evaluation were cut from unused oilfield pipes and had surface areas of
approximately 4.4 in
2
. Each test metal coupon was prepared by degreasing with acetone, bead-blasting,
and washing with water and acetone in a sequence. The preweighed metal coupons were suspended in
glass cells using Teflon

tape. The glass cells were filled with the test solution and covered with a glass
cap. The glass cells were inserted into a small Hastelloy B-2 autoclave, along with mineral oil as a
heat-transfer medium. The autoclave was pressurized to 1,000 psi with nitrogen. The pressure was
maintained using a backpressure regulator assembly, which allowed for automatic bleed off of excess
pressure that can develop during heating and release of corrosion products. The autoclave was heated in
a heating jacket, and the temperature of the test solution was regulated using Eurotherm controllers. The
total test time included the 75 min of heat-up time and 15 min of cool-down time.
After the test, a suspended coupon was removed and washed with a soft brush using mild abrasive
cleaning powder and then acetone. The dried coupon was again weighed. Corrosion weight loss is
expressed in lbm/ft
2
as ratio of weight loss to the total surface area of the coupon.
The corrosion loss in units of lbm/ft
2
can be calculated using the following equations:
(1)
Where S.A. in
2
is the surface area of a coupon measured in square inches, W1 is the weight in
grams of the coupon before testing, and where W2 is the weight in grams of the coupon after testing.
Table 1Chemical Compositions of Alloys Used
SPE-169637-MS 3
According to this method, the typical industry standard for an acceptable corrosion loss of carbon steel
alloy is less than or equal to 0.05 lb/ft
2
under the design conditions of acid and concentration and of fluid
contact time at a specified temperature and pressure.
Mixing of Acid Test Solution
The following order of mixing was used for preparing the test solutions:
1. Base fluid (water or 1.04 SG NaCl brine as applicable).
2. Corrosion inhibitor intensifier (CII-1) if applicable.
3. Corrosion inhibitor (solid (SCI) / liquid extract (LCI)).
4. Corrosive media (concentrated HCl / organic acid mixture).
5. Corrosion inhibitor intensifier (CII-2), if applicable.
Results and Discussion
Application of Solid Plant-Based Corrosion Inhibitor in Mineral and Organic Acids
Inhibition efficiency of SCI was tested on N-80 carbon steel alloy following the static weight-loss
corrosion method. Because acids, such as 7.5% HCl and organic acids, are typically used for activities,
such as prejob pickling, scale removal, and near-wellbore (NWB) damage removal, tests were performed
using a 7.5% HCl and an organic acid mixture, respectively, as the corrosive media. Addition of 15% HCl
was included in the test plan because it is a routine recipe for matrix stimulation jobs. Corrosion inhibitor
SCI and the other applicable additives were mixed in the respective acids following the mixing order
mentioned. A duration of 6 hrs was assumed to be sufficient for a typical acidizing job; hence, all the tests
were performed for a total duration of 6 hrs to generate comparative data and define guidelines.
Table 2 depicts the results of tests performed using 15% HCl as the corrosive media. While 3.0
lbm/Mgal of SCI was sufficient to inhibit corrosion (0.0233 lb/ft
2
) with 7.5% HCl acid at 150F; 4.0
lbm/Mgal of SCI was required to achieve a pass at the same concentration at 175F. When the acid
concentration and test temperature were increased to 15% HCl and 200F, respectively, 50 lbm/Mgal of
SCI had to be intensified by incorporating 20 lbm/Mgal of CII-1 to achieve a pass (0.0408 lbm/ft
2
).
Table 3 depicts the results of tests performed using an organic acid mixture of 13% acetic acid along with
9% formic acid. This organic acid mixture was selected because a mixture of 13% acetic acid and 9% formic
acid has equivalent dissolution power to 15% HCl and is typically used for pickling and carbonate scale
removal jobs. 1.04 SG NaCl brine (~2.5%) was used as a clay stabilizer in the organic acid test recipes.
A test recipe of 50 lbm/Mgal of SCI intensified with 20 lbm/Mgal of CII-1 resulted in a pass in the
temperature range of 200 to 250F for 6 hrs. At higher temperatures, amounts of the inhibitor and intensifier
had to be increased, as expected. At 275F, 75 lbm/Mgal of SCI intensified with 100 lbm/Mgal of CII-1
resulted in a pass (0.0270 lbm/ft
2
). This recipe, however, failed to effectively inhibit corrosion at 300F.
Table 2Corrosion Testing with Sci in Hcl Acid*
*All tests were performed for total test duration of 6 hrs and on N-80 carbon steel alloy.
4 SPE-169637-MS
Application of Liquid Plant-Based Corrosion Inhibitor in Mineral and Organic Acids
Inhibition efficiency of LCI was tested on various carbon steel alloys. Testing was performed on N-80
alloy upto a maximum of 300F. Other alloys tested included QT-800, 13Cr-L80, and P-110. The
13Cr-L80 is a low alloy steel routinely used in oilfield applications. P-110 is also a low alloy high-strength
carbon steel typically used in deep sweet oil and gas wells with high pressures.
For tests with 15% HCl as the corrosive media, 5% LCI intensified with 100 lbm/Mgal CII-1 was able
to successfully inhibit corrosion upto 250F. Beyond this temperature, it was difficult to inhibit corrosion
and all attempts to use LCI as inhibitor failed. Even with a maximum of 15% LCI intensified with 120
lbm/Mgal of CII-1, corrosion losses in excess of 0.05lbm/ft
2
were observed (Table 4).
Probable Mechanism for Inhibitive Action
Structurally, the plant-based material evaluated for corrosion inhibition is composed of steroidal lactones.
Steroidal lactones consist of C
28
steroid backbone bound to a sixmembered lactone ring. For example,
steroidal lactones can be ergostane type steroids with a C
28
basic skeleton with a side chain of C
9
units
in which a six-membered lactone ring is included. Steroidal lactones include a group of at least 300
naturally occurring chemical compounds. Steroidal lactones occur as secondary metabolites primarily in
genera of the Nightshade family of plants. In addition to steroidal lactones, evaluated material also
contains some alkaloids. Steroidal lactones have oxygen (O) atoms whereas alkaloids have nitrogen (N)
and sulfur (S) atoms as heteroatoms. By virtue of the presence of these heteroatoms, it is proposed that
the corrosion inhibition action of the discussed material is attributed to adsorption of the steroidal lactones
and alkaloid molecules on the surface of the tested carbon steels. Further, it is proposed that the
Table 3Corrosion Testing with Sci in Organic Acid*
*All tests were performed for total test duration of 6 hr and on N-80 carbon steel alloy.
*Organic acid mixture was 13% acetic acid 9% formic acid. The mixture was prepared in 1.04 SG NaCl brine.
Table 4Corrosion Testing with Lci in Hcl Acid
SPE-169637-MS 5
hydrocarbon based backbone/skeleton and side chains in these molecules can also act as a hydrophobic
barrier between the metal surface and the media and thus inhibit corrosion. Thus, the entire structure of
steroidal lactone and alkaloid adsorbed on the surface through the heteroatoms and the hydrophobic
backbone can block the contact of discharged Hions from acid with the metal surface, thereby inhibiting
the electrochemical reaction between acid and metal.
Fig. 1 is the schematic representation of adsorption mechanism of corrosion inhibitor on the metal
surface. While Fig. 2 present a typical N-80/P-110 coupon before and after treatment with acid.
Conclusions
The information presented can serve as a guide for the use of this environmentally acceptable plant-based
corrosion inhibitor. Both the solid powder and liquid extract forms of the inhibitor chemical retrieved from
the plant are available for use and can successfully inhibit corrosion. SCI was able to inhibit 15% HCl upto
200F and the organic acid mixture of 13% acetic acid and 9% formic acid upto 275F on N-80 alloy. LCI,
on the contrary, successfully inhibited 15% HCl upto 250F on N-80 and QT-800 alloys. It is proposed
that this inhibition action is attributed to the adsorption of structural features of the chemical on the metal
surface, thereby creating a barrier for the H ions. This adsorption is facilitated through the presence of
heteroatoms on the chemical structure.
Acknowledgements
The authors thank Halliburton for permission to publish this work.
Figure 1Schematic representation of adsorption mechanism of corrosion inhibitor on the metal surface.
Figure 2Typical N-80/P-110 coupon before and after treatment with acid.
6 SPE-169637-MS
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