Corrosion Resistance by SPT E-ISSN:

Christy et al.

Corrosion Resistance Of Mild Steel In Simulated Produced

Water In Presence Of Sodium Potassium Tartrate

A.Christy Catherine Mary[a] , S.Rajendran[b], Hameed Al-Hashem[c], R.Joseph

Rathish[d], T. Umasankareswari[e] and J Jeyasundari[f]

Corrosion behavior of mild steel (MS) in simulated produced water (SPW) has been evaluated by AC impedance
spectra. The influence of sodium potassium tartrate (SPT) on the corrosion resistance of mild steel in SPW has also
been investigated. When 5000 ppm of SPT is added the corrosion resistance of MS decreases. Further, when 10000
ppm of SPT is added the corrosion resistance further decreases. This is revealed by decrease in charge transfer
resistance (Rt), decrease in impedance value and increase in double layer capacitance (Cdl).

Keywords: Simulated produced water, corrosion, mild steel, sodium potassium tartrate.

* Corresponding Authors

[a] PG Department of Chemistry , Sakthi College of Arts and Science for Women , Ottanchatram, Tamil Nadu, India.
Email: chriscethi@gmail.com
[b] Corrosion Research Center ,Department of Chemistry, RVS School Of Engineering and Technology, Dindigul – 62405
Tamil Nadu, India, Email: susairajendran@gmail.com
[c] Senior Research Scientist, Petroleum Research Center, KISR, Kuwait. Email: ahashem-kisr@hotmail.com
[d] PSNA College of Engineering and Technology, Dindigul, Tamil Nadu, India.
[e] Department of Chemistry, Rajapalyam Rajus College, Rajapalayam, India
[f] PG and Research Department of Chemistry, SVN College, Madurai, India

1. INTRODUCTION
Produced water is water trapped in underground formations that is brought to the surface during oil and gas
exploration and production. In traditional oil and gas wells, produced water is brought to the surface along with
oil or gas. In coal bed methane production, wells are drilled into coal seams, and the water located there is
pumped to the surface in order to allow gas to release from the coal seams. Because the water has been in contact
with the hydrocarbon-bearing formation for centuries, it has some of the chemical characteristics of the
formation and the hydrocarbon itself. It may include water from the reservoir, water injected into the formation,
and any chemicals added during the drilling, production, and treatment processes. Produced water can also be
called "brine", "saltwater", or "formation water."

The physical and chemical properties of produced water vary considerably depending on the geographic
location of the field, the geological formation from which it comes, and the type of hydrocarbon product being
produced. Produced water properties and volume can even vary throughout the lifetime of a reservoir.

The major constituents of interest in produced water are,

Salt content: Salt content can be expressed as salinity, total dissolved solids, or electrical conductivity. The
salt content in produced water varies widely, from nearly freshwater to salt levels up to ten times higher than
seawater.

Oil and grease: Oil and grease is not an individual chemical. Rather, the term "oil and grease" refers to a
common test method that measures many types of organic chemicals that collectively lend an "oily" property to
the water.

Various inorganic and organic chemicals: These chemicals are found naturally in the formation, are
transferred to the water through long-term contact with the hydrocarbon, or are chemical additives used during

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drilling and operation of the well. The presence of specific chemicals and the concentrations of those chemicals
vary widely among different produced water samples.

Naturally occurring radioactive material (NORM): Some of the formations holding oil and gas have
small concentrations of natural radioactivity. Low levels of the radioactivity can be transferred into produced
water. Generally, the radiation levels in produced water are very low and pose no risk. However, scale from
pipes and sludge from tanks holding produced water can concentrate NORM.

Inhibition of scale buildup and optimization of the selected compound inhibitor have been
investigated during the recycling and reuse of oilfield produced-water. Particular attentions were paid to the
factors of scale inhibition, and the changes of scale phase composition and morphology. The results showed that
the addition of Zn2+ ions can effectively inhibit the process of corrosion, and then reduce scale growth. A
dispersing agent was required to buffer against the adhesion of crude oil with the precipitates. The
compound inhibitor (ratio of PBTCA, HEDP and ATMP, 2:2:1) achieved a higher efficiency of scale inhibition
(97.34%) than any of the inhibitors individually. Moreover, structural anomalies of the crystals also revealed
significant differences in the presence and absence of the compound inhibitor. The results proved that the
pipelines first corrode, then, mechanical impurities,residual petroleum hydrocarbons and calcium scale gradually
attach to the corrosion point to form a dirt scale layer. After n periods, a bedding black-and-white scale layer
forms. During the field trial, it was found that dosing the compound inhibitor at 70ppm results in a 92.46%
inhibition efficiency (IEs) at 85°C. Therefore, the compound inhibitor could be applied to prevent the buildup of
scale during produced-water [1].

Within the Middle East region the development of large gas accumulation has resulted in a need for hydrate
control within the produced fluids during the winter months. Development of kinetic hydrate inhibitors (KHI) as
an alternative to thermodynamic hydrate inhibitors (THI) such as methanol or mono ethylene glycol (MEG) has
resulted in a significant reduction in process equipment size and associated operational costs but the disposal of
the resulting KHI that predominately part ions into the produced water and corrosion inhibitor constantly added
to production lines has raised concerns about formation damage within the injection/disposal wells under matrix
flow conditions This paper will present details from a set of core floods which look at produced water re
injection (PWRI) under matrix flow conditions within carbonate cores and the observed damage such KHI and
KHI/CI solutions can produce within Arab D formation rock. The core flood tests generated pressure profiles,
cation, pH and KHI concentration within the core flood effluent during the injection of these fluids to fully
understand the process occurring within the rock (dissolution, ion exchange, precipitation/adsorption, filtration).
The study then looked at mitigation methods for the damage that could be potentially induced and then based on
understanding the two generations of KHI and associated corrosion inhibitor molecule structure what changes
could be made to the produced fluid composition to eliminate the damage from forming in the first place[2].

The calcium and bicarbonate ions, present in the produced waters in the oilfields, are two major scaling ions
in CaCO3 formation. In the last decade, a lot of studies have been focused on the thermodynamic or kinetics of
CaCO3 formation, including the effects of scaling ions, temperature, pH, pCO 2, etc. Seldom studies are focused
on the kinetics of calcium carbonate surface deposition with different levels of calcium and bicarbonate,
especially in the presence of scale inhibitors. In the work reported herein, dynamic loop tests were carried out to
study the kinetics of CaCO3 surface deposition in three typical produced waters (Water-1, high calcium and low
bicarbonate; Water-2, medium calcium and medium bicarbonate; Water-3, low calcium and high bicarbonate)
with same saturation index (SI) at 150°C. Typical scale inhibitor chemistries, including phosphonate,
polycarboxylic, polymaleic, polysulphonate, polyacrylic, polyaspartate based scale inhibitors, have been tested
in three tested waters. The following conclusions are drawn based on the test results.

• SI generated by applied prediction software is a parameter indicating the thermodynamic driving force.
The kinetics of scale formation, more representative field conditions, should be studied as well to give a
guideline of scale formation in the fields.

• Comparison of calcium, bicarbonate is the dominant kinetic factor for CaCO 3 formation in the absence and
presence of inhibitors.

• Higher bicarbonate water, higher minimum inhibitor concentration (MIC) is requested, even the three
tested waters with a same SI.

• The ranking of the performance of scale inhibitor are dependent on the water chemistries
and inhibitor chemistries. Some of the best ranking phosphonates in Water-1 and Water-2 with low and medium

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bicarbonate showed poor performance on Water-3 with high bicarbonate. Some polymers showed contrary
ranking performance. This paper gives a comprehensive study of the kinetics of CaCO3surface deposition
considering the effects of calcium and bicarbonate, including prediction, laboratory evaluation, mechanisms
and inhibitor selection. It will contribute to understand the kinetics of CaCO 3 formation and recommend
effective inhibitors for field application. Environmentally acceptable inhibitors have been developed for different
CaCO3 water chemistries at elevated temperature and are suitable for applications through squeeze treatment or
continuous injection [3].

Scale inhibitors are used extensively in the oil and gas industry to provide the level of flow assurance
required to maximize safe and economic hydrocarbon production. For both continuous and scale squeeze
treatments, residual inhibitor concentrations need to be verified on a continual basis to assure the field operator
that the implemented scale management program remains effective. To date, the analytical work required to
verify residual inhibitor levels of the majority of scale inhibitor chemistries needs to be carried out onshore in a
suitably equipped analytical laboratory [4].

With wet tree developments now outweighing dry tree developments in the North Sea, the challenge of
accurate surveillance of scaling in wells is increasing. Often, multiple wells feed into manifolds which
themselves feed into comingled systems. The need to differentiate multiple scale inhibitor molecules in the same
sample of produced water is now essential in order to monitor the scale health of any given well in that system.
Accurate surveillance can save potentially millions of dollars of deferred oil production, intervention vessel hire
and chemical and operational costs [5].

The emulsion stability of oilfield produced water is related to the oil-water interfacial film strength and the
zeta potential of the oil droplets. We investigated the effects of water treatment agents (corrosion inhibitor SL-2,
scale inhibitor HEDP, germicide 1227, and fiocculant polyaluminium chloride PAC) on the stability of
oilfield produced water. The influence of these treatment agents on oil-water interfacial properties and the
mechanism of these agents acting on the oilfield produced water were studied by measuring the interfacial shear
viscosity, interfacial tension and zeta electric potential. The results indicated that the scale inhibitor HEDP could
increase the oil-water interfacial film strength, and it could also increase the absolute value of the zeta potential
of oil droplets. HEDP played an important role in the stability of the emulsion. Polyaluminum chloride (PAC)
reduced the stability of the emulsion by considerably decreasing the absolute value of the zeta potential of oil
droplets. Corrosion inhibitor SL-2 and germicide 1227 could decrease the oil-water interfacial tension, whereas
they had little influence on oil-water interfacial shear viscosity and oil-waterinterfacial electricity properties [6].

The produced water from five joint stations of Jiangsu Oilfield have been used to carry out the
denitrification static test. The effects of inhibitor addition with different concentrations, forms, ratios and pulsing
DNB on bacterial number of SRB and DNB, the amount of hydrogen sulfide and redox potential were studied .
The results showed that the addition of nitrate, nitrate and molybdate can inhibite the growth of SBR in
oilfield produced water, and with the same concentration, the inhibition effect of nitrite is the best, and nitrate is
the second. The addition of pulsing DNB and 0.3~0.5 g/L nitrite/nitrate (the ratio is 1:1) can effectively inhitite
the generation of SRB and hydrogen sulfide, in which the concentration of 0.5 g/L has the best inhibition effect,
the time can be more than 10 d, and the inhibition rate of SRB and hydrogen sulfide can reach 87% and 98%,
respectively. The atmospheric static corrosion test showed that the corrosion rate of inhibitors is higher than that
of bactericide and corrosion inhibitor, but lower than the standard of petroleum and natural gas industry(0.0076
mm/a)and that of the contrast sample(0.152 mm/a) [7].

Carbonate and sulfate scales formed on oilfields under natural depletion or water injection support, can
occur on a number of critical points from the reservoir to topside facilities impacting on well productivity. Scale
control has become a challenging task as oil industry tends to go for deeper water with complex completion
wells which may produce from harsh environment conditions (HP, HT). Scale management has become a power
tool to assure that oil loss due to precipitation along oil production process be avoided and costs associated to its
prevention and remediation treatments be minimized [8].

The present work is under taken to evaluate the corrosion resistance of mild steel in simulated produced
water (SPW) by electro chemical study, namely, AC impedance spectroscopy. The influence of sodium
potassium tartrate (SPT) on the corrosion resistance of mild steel in simulated produced water will also be
investigated.

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2. EXPERIMENTAL PROCEDURE
Simulated produced water was used in the present study. The composition of the solution is ; CaCl2 15
g/l; NaHCO3 1.1g/l with a pH of 6.5 [9].

2.1 AC Impedance Measurements:

A three electrode cell assembly was used (fig 1). Mild Steel was used as working electrode. Platinum foil
was used as counter electrode. Saturated calomel electrode (SCE) was used as reference electrode.

Fig.1 Three electrode cell assembly

A CHI electro chemical analyzer (model 660A) was used for AC impedance measurements. A time interval
of 5 to 10 minutes was given for the system to attain its open circuit potential. The real part Z’ and imaginary
part Z’’ of the cell impedance were measured in Ohms at various frequencies. The values of the charge transfer
resistance Rt, double layer capacitance Cdl and impedance value were calculated.

Rt = (Rs+ Rt) – Rs ------------- (1)

where Rs= solution resistance

Cdl = ½ π Rtfmax --------------(2)

Where fmax = maximum frequency

AC impedance spectra were recorded with initial E(v) = 0; high frequency (Hz) = 1;

amplitude (v) = 0.05; and quiet time(s) = 2.

3 RESULTS AND DISCUSSION

3.1 Analysis of AC Impedance Spectra:

AC impedance spectra (electro chemical impedance spectra) have been used to confirm the formation of
protective film on the metal surface [10 –18]. If a protective film is formed on the metal surface, charge transfer
resistance (Rt) increases; double layer capacitance value (Cdl) decreases and impedance log (z/ohm) value
increases. The phase angle also increases. The AC impedance spectra of carbon steel immersed in simulated
produced water in the presence and absence of SPT are shown in figure 2 to 7.

The AC impedance parameters namely charge transfer resistance (R t) and double layer capacitance (Cdl)
were derived from Nyquist plots. The impedance log (z/ohm) values were derived from Bode plots.

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It is observed that when 5000 ppm of SPT are added, the charge transfer resistance (R t) decreases from
84303 ohm cm2 to 1030.1 ohm cm2 . When 10000 ppm of SPT are added, the charge transfer resistance (R t)
decreases from 84303 ohm cm2 to 315.9 ohm cm2. The decrease in Rt value indicated that the rate of corrosion
increase when SPT is added. So, care must be taken to avoid inclusion of SPT into simulated produced water
during operation.

This view is supported by the fact that when 5000 ppm of SPT is added, the double layer capacitance
(Cdl)value increases from 4.115x10-9 F/cm2 to 3.368 x10-9 F/cm2. Similarly, when 10000 ppm of SPT is added,
the double layer capacitance value (Cdl) increases from 4.116x10-11 F/cm2 to 1.984 x10-8 F/cm2. This is futher
supported by decrease in impedance value.

When 5000 ppm of SPT is added, the impedance value decreases from 4.987 to 2.993 [log(z/ohm)].
Similarly, when 10000 ppm of SPT is added, impedance value decreases from 4.987 to 2.725 [log(z/ohm)].
These results lead to the conclusion that a protective film is not formed on the metal surface. Further, SPT could
not be included in the MS pipeline carrying produced water.

Fig.2 AC impedance spectrum (Nyquist plot) of mild steel immersed in SPW

Fig .3 AC impedance spectrum (Nyquist plot) of mild steel immersed in SPW containing 5000 ppm of SPT

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Fig .4 AC impedance spectrum (Nyquist plot) of mild steel immersed in SPW containing 10000 ppm of SPT

Fig .5 AC impedance spectrum (Bode plot) of mild steel immersed in SPW

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Fig .6 AC impedance spectrum (Bode plot) of mild steel immersed in SPW containing 5000 ppm of SPT

Fig .7 AC impedance spectrum (Bode plot) of mild steel immersed in SPW containing 10000 ppm of SPT

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Table 1: Corrosion parameters of carbon steel immersed in simulated produced water in the absence and presence of Sodium
potassium tartrate obtained from AC impedance spectra (pH = 6.5)

Nyquist plot Bode plot

S.No System

Rt ohm cm2 CdI F/ cm2 Impedance value

log(z/ohm)
Simulated produced water
1 84304 4.116x10-11 4.987

Simulated produced water +

2 SPT 5000ppm 1030.1 3.368x10-9 2.993

Simulated produced water +

3 SPT 10000ppm 315.9 1.984x10-8 2.725

4. CONCLUSION

 Corrosion behavior of mild steel in simulated produced water (SPW) has been evaluated by AC
impedance spectra.

 The influence of sodium potassium tartrate (SPT) on the corrosion resistance of mild steel has also
been investigated.

 When 5000 ppm of SPT is added the corrosion resistance of MS decreases.

 Futher when 10000 ppm of SPT is added the corrosion resistance futher decreases.

 This is revealed by decrease in charge transfer resistance (Rt), decrease in impedance value &
increase in double layer capacitance (Cdl).

 So, the inclusion of sodium potassium tartrate (SPT) in the pipeline carrying simulated produced
water (SPW) should be avoided.

5. ACKNOWLEDGEMENT

The authors are thankful to their respective managements, Dr. Mary Josephine Isabella Principal of Sakthi
College of Arts and Science for Women, Oddanchatram, Dindigul, Tamil Nadu, India and Dr. R.Saravanan,
Director of RVS School Of Engineering and Technology, Dindigul, Tamil Nadu, India.
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Received: (20-01-2015)
Accepted: (18-02-2015)

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