Preventing coiled tubing corrosion by

hydrochloric acid in hot wells

Achala Danait Surachai Kanchiak . World Oil ; Houston (Mar 2011): n/a.

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ABSTRACT
 
Various forms of corrosion, internal and external, can occur with the use of coiled tubing (CT) in oilfield operations.
One common source of corrosion results from the use of hydrochloric (HCl) acid. Lab testing revealed chemistries
capable of maintaining CT integrity while allowing HCl acid concentrations sufficient to dissolve calcium
carbonate scales.

FULL TEXT
 
Lab testing revealed chemistries capable of maintaining CT integrity while allowing HCl acid concentrations
sufficient to dissolve calcium carbonate scales.
Vol. 232 No. 3
COILED TUBING TECHNOLOGY
Preventing coiled tubing corrosion by hydrochloric acid in hot wells
Lab testing revealed chemistries capable of maintaining CT integrity while allowing HCl acid concentrations
sufficient to dissolve calcium carbonate scales.
Achala Danait, Jay Elliott* and Anupom Sabhapondit, Halliburton; and Surachai Kanchiak, Chevron Thailand
Exploration and Production (CTEP)
Various forms of corrosion, internal and external, can occur with the use of coiled tubing (CT) in oilfield operations.
One common source of corrosion results from the use of hydrochloric (HCl) acid, which is often pumped through or
around the CT as part of a typical treatment. This exposes both internal and external faces of the CT to the acid's
corrosive effects; for this reason, the control and prevention of acid-related corrosion on CT is critical to help
prevent costly and dangerous CT failures. However, at this time, little research exists on the prevention of HCl acid
corrosion at temperatures greater than 350[degrees]F.
Asia-Pacific operators routinely use CT for various acidizing applications, including calcium carbonate scale
removal. These treatments require high concentrations of HCl acid (about 15%), at depths where temperatures can
reach 425[degrees]F. Controlling CT corrosion from HCl acid at these high temperatures is a serious concern,
particularly because few high-temperature corrosion inhibitors are available.
Using one of the most widely applied CT alloys, QT-800, researchers tested the effectiveness of various acid-
corrosion inhibitors and the resulting HCl acid concentrations required to provide adequate corrosion protection up
to 450[degrees]F. In most cases, it was found that the performance of a quaternary amine-based corrosion
inhibitor was comparable to a propargyl alcohol-based corrosion inhibitor. The addition of an antimony-based
intensifier to the acid blend was also necessary to achieve low corrosion losses. Furthermore, as temperatures
approached 425[degrees]F, reducing the HCl acid concentration to as low as 5% was required to achieve an HCl
acid blend capable of dissolving calcium carbonate scale while maintaining the industry-acceptable corrosion-loss
values of 0.05 lb/sq ft or less. This research will help ensure continued safe use of the CT through successive HCl
acid treatments in high-temperature wells.

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INTRODUCTION
The alloy QT-800 is classified as a modified ASTM A-606, Type 4, high-strength, low-alloy steel. Type 4 steels
contain additional alloying elements, along with copper, which provides a level of corrosion resistance
substantially better than that of carbon steels with or without copper addition. These steels are therefore a
preferred choice for CT.
Electrochemical tests using new and cycled CT-90 and CT-100 in various common oilfield fluids suggest that CT
corrosion tendency is not significantly accelerated as a result of cycling at low temperatures of 100[degrees]F.1
However, at 295[degrees]F, significantly higher corrosion rates were observed for both cycled CT-90 and cycled CT-
100. This reduced resistance of fatigued coil underlines the importance of correctly protecting the CT against
corrosion at elevated temperatures.
Corrosion inhibitors can be broadly classified into two types: anodic and cathodic. Anodic inhibitors function by
sharing electrons with anodic sites at the metal surface, forming a dative bond. Cathodic inhibitors function by
forming a protective film on the metal surface by attracting the inhibitor to cathodic areas through electrostatic
attraction.2
Arsenic compounds were commonly used as corrosion inhibitors for HCl acid until concerns about toxicity led to
their elimination. The next generation of corrosion inhibitors used acetylenic alcohols and coal-tar derivatives
blended with solvents and dispersants. Quaternary-ammonium compounds have also demonstrated promising
inhibition behavior.
At especially high temperatures (when corrosion is most severe), certain additives are required. These additives,
referred to as intensifiers, cannot be considered inhibitors when used alone, but can improve the effectiveness of
organic inhibitors when used with them. The commonly used intensifiers are copper salts, potassium iodide,
formic acid and antimony compounds. Copper salts as inhibitor aids are not preferred because of environmental
concerns. Antimony salts exhibit excellent intensifier properties at HCl acid concentrations below 17% and
temperatures above 250[degrees]F.3
TESTING
Few acid-corrosion inhibitors and intensifiers have been screened for testing at the high-temperature range from
250 to 450[degrees]F. The objective of this study was to design an acid blend that could provide adequate
corrosion protection for QT-800 alloy when exposed to high temperatures (up to 450[degrees]F) for a period of 4 hr,
while at the same time remaining effective in the primary goal of dissolving calcium carbonate scales. The
targeted maximum corrosion loss for this testing was 0.05 lb/sq ft with no pitting. The selected inhibitors and
intensifiers with their general chemical nature are listed in Table 1.
TABLE 1. Selected corrosion inhibitors and intensifiers
Propargyl alcohol-based materials have been widely used to provide corrosion inhibition at elevated
temperatures,4 and so were chosen as the initial inhibitor for testing purposes. Regarding the intensifiers, because
of the high bottomhole temperatures of the study and HCl acid concentrations below 17%, antimony salts were
preferred for initial testing because of their advantages under similar test conditions.3
Dosages of the corrosion inhibitors and intensifiers are based on the commercial blends available and not on a
pure material basis. All inhibitor and intensifier concentrations are reported in volume percentages of the total acid
blend. Surfactants and penetrating agents were used as per industry norms and kept constant in all experiments.
Different corrosion behaviors can be obtained under the same test conditions, if the same grade of CT is procured
from different sources. To minimize variation, the test specimens were obtained from the actual QT-800 CT used
on location, and the same sample source was used for all testing coupons. The typical metallurgy of QT-800 is
presented in Table 2.
The QT-800 tubing used for testing had a 1.296-in. ID, 0.102-in. wall thickness and 1.5-in. OD, and was cut into
cylindrical coupons with a height of 0.4 in. and a surface area of 4.4 sq in. Care was taken to ensure that the
coupon was not heated during the deburring process because this could change the properties of the metal.
Acid-corrosion testing was conducted using small Hastelloy B-2 autoclaves, which test one specimen at a time.

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The coupons were initially degreased with acetone and then bead-blasted. The initial weight of each coupon was
recorded, and then the coupon was suspended in a 125-ml glass cell with the help of Teflon tape, and 100 ml of
acid blend was placed in the cell. After capping the cell, the remaining autoclave volume was filled with mineral oil,
which acts as a heat-transfer medium, and the cell contents were pressurized to 1,000 psi with nitrogen. Pressure
was maintained using a backpressure regulator assembly, which allows for automatic bleed-off of excess pressure
developed during heating and release of corrosion products. The autoclaves were heated using Eurotherm
controllers. The contact times included a 75-min. heat-up time and a 15-min. cool-down time.
After each test, the autoclave was first allowed to cool slowly at room temperature and then was cooled in water.
The pressure was released, and the glass cell was carefully removed. The coupon was cleaned with a soft brush
using a mildly abrasive cleaning powder, washed with water and rinsed with acetone. The coupon was dried and
the final weight was recorded.
Temperature effects. Figure 1 illustrates the static high-pressure/high-temperature (HPHT) corrosion-loss data at
temperatures from 250 to 400[degrees]F. Acid blends with 15% and 17% HCl acid containing propargyl alcohol-
based inhibitor (Inhibitor-P) and antimony-based intensifier (Intensifier-1) were tested for 4 hr.
Up to 325[degrees]F, acceptable corrosion-loss values (0.05 lb/ft or less) could be achieved using 17% HCl and 2%
each of Inhibitor-P and Intensifier-1. From 325 to 350[degrees]F, adequate corrosion protection was obtained by
either decreasing the HCl acid concentration to 15% or by increasing the concentrations of Inhibitor-P and
Intensifier-1 to 4% each. At 375[degrees]F, 15% HCl acid and 4% each of Inhibitor-P and Intensifier-1 were required
to achieve acceptable corrosion-loss values.
The corrosion loss increased sharply above 375[degrees]F, requiring the use of lower acid concentrations for the
acid blends.
HCl concentration effects. Figure 2 presents the static HPHT corrosion-loss data at temperatures from 375 to
400[degrees]F. Acid blends with HCl acid concentrations below 15% were tested with Inhibitor-P and Intensifier-1
for 4 hr.
The corrosion loss increased drastically above 375[degrees]F, as expected. An HCl acid concentration of 10% was
necessary to adequately protect the QT-800 alloy at 400[degrees]F, while an HCl acid concentration as low as 5%
was required to enable the Inhibitor-P/Intensifier-1 pair to inhibit the acid suitably at 425[degrees]F. At these high
temperatures, the inhibitor and intensifier concentrations were maintained at 4% each. Because the results
achieved were near the limit of this inhibitor-intensifier system, it was decided to additionally investigate the
behavior of a quaternary-ammonium salt-based inhibitor (Inhibitor-Q).
TABLE 2. Typical metallurgy and properties of QT-800
coiled tubing
TABLE 3. HPHT corrosion-loss data with Inhibitor-Q at 400[masc ordinal]F after 4 hr
TABLE 4. Effect of different intensifiers on corrosion loss in
15% HCl acid at 400[degrees]F after 4 hr

Fig. 1. Effect of temperature from 250 to 400[masc ordinal]F on corrosion loss for 4 hr.            

Fig. 2. Effect of HCl concentration on corrosion loss for 4 hr.            

Inhibitor-Q effects at 400[degrees]F. Quaternary amines have long been known as excellent corrosion inhibitors for
their ability to form a film on the steel surface.5,6 To evaluate the effectiveness of the quaternary-ammonium salt-
based inhibitor on corrosion loss at high temperatures, it was decided to use this inhibitor, Inhibitor-Q, in
conjunction with Intensifier-1, which was used in earlier tests. HPHT corrosion-loss data are presented in Table 3.
Using 15% HCl acid and the same concentration (4%) of inhibitor as in previous tests, it was observed that at
400[degrees]F, Inhibitor-Q provided slightly better corrosion protection than Inhibitor-P. Increasing the Inhibitor-Q
concentration to 5% did not result in any improvement in the corrosion-loss values. A reduction in HCl acid

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concentration below 15% had higher corrosion-loss values when the Inhibitor-Q and Intensifier-1 concentrations
were maintained constant at 4% each. This trend was not observed for the Inhibitor-P/Intensifier-1 combination.
Further investigations should be conducted to identify the cause of this anomalous behavior.
Intensifier variation effects. Three other commonly available intensifiers were tested at high temperatures with QT-
800 alloy: Intensifier-2, an alkali iodide-based material; Intensifier-3, an organic acid-based material; and Intensifier-
4, an organic phosphonium chloride-based material. All these intensifiers are generally recommended for high-
temperature applications.
As shown in Table 4, Intensifiers-2, -3 and -4 showed much higher corrosion losses than Intensifier-1. Thus, the
antimony-based Intensifier-1 is the most effective intensifier when used in combination with either the propargyl
Inhibitor-P or the quaternary ammonium-based inhibitor-Q.
CONCLUSIONS
Based on these results, it is now possible to protect the QT-800 alloy from HCl acid corrosion at temperatures up
to 425[degrees]F. This can be achieved through the combined use of Inhibitor-P and Intensifier-1, along with the
reduction in HCl acid concentration down to 5% as the temperature is increased. However, reducing the HCl acid
concentration to this degree will also reduce the dissolution power of the resulting HCl acid blend, requiring higher
volumes of acid to dissolve the calcium carbonate scales. In situations where pumping high volumes of acid is not
practical, an organic acid blend having a dissolving power equivalent to 15% HCl acid can be considered as an
alternative to HCl acid when the temperature reaches 425[degrees]F or higher.
ACKNOWLEDGMENTS
This article was prepared from a poster presented at the 15th SPE/ICoTA European Well Intervention Round Table
held in Aberdeen, UK, Nov. 18-19, 2009. The authors thank the management of Halliburton and Chevron for
permission to present these findings. Efforts taken by Giselle Braganza, Jajati Nanda and Balakrishnan
Shanmugaraj for the lab work are greatly appreciated.
LITERATURE CITED
1 Van Arman, W., McCoy, T., Cassidy, J. and R. Rosine, "The effect of corrosion in coiled tubing and its prevention,"
SPE 60744 presented at the SPE/ICoTA Coiled Tubing Roundtable, Houston, Texas, April 5-6, 2000.
2 Foster, G., Oakes, B. and C. Kucera, "Acetylenic corrosion inhibitors," Industrial &Engineering Chemistry, 51, No. 7,
1959, pp. 825-828.
3 Walker, M., "Method and composition for acidising subterranean formations," US Patent No. 4498997, 1985.
4 Aramaki, K. and E. Fujioka, "Spectroscopic investigations on the inhibition mechanism of propargyl alcohol for
iron corrosion in hydrochloric acid at elevated temperatures," Corrosion, 53, No. 4, 1997, pp. 319-326.
5 Tiwari, L., "Design and development of quaternary amine compounds: Corrosion inhibitors with improved
environmental profiles," SPE 95081 presented at the International Symposium on Oilfield Corrosion, Aberdeen, UK,
May 13, 2005.
6 Katheeri, M. and H. Nasr-El-Din, "Application of CE and CE-MS to assay corrosion inhibitors used in well
stimulation treatments," SPE 95112-MS presented at the International Symposium on Oilfield Corrosion, Aberdeen,
UK, May 13, 2005.
THE AUTHORS
Achala Danait earned a PhD degree in polymer chemistry from the Indian Institute of Technology in Mumbai. She
began her career in academics as an Assistant Professor of polymer chemistry and also worked on government-
sponsored research projects. After nine years in academics, she joined Sudarshan Chemical Industries Ltd. as a
Senior Manager of R&D. During her five years in that position, she conducted research on phthalocyanine
pigments. In 2007, she joined the Halliburton Technology Center in Pune, India, where she is now the Technology
Leader of the Production Enhancement team, which provides technical services to the Eastern Hemisphere.
Jay Elliott earned a mechanical engineering degree from the University of Alberta in Edmonton. He began his
oilfield career working in measurement-while-drilling applications and later became involved with fracturing and
coiled tubing. He has worked throughout Northern Canada and Thailand, and currently resides in Vietnam, where

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he is the Senior Well Operations Engineer for Korea National Oil Corporation.
Anupom Sabhapondit earned a PhD degree in chemistry from Dibrugarh University in Assam, India. He worked for
Dai-Ichi Karkaria Ltd. in Pune, India, as an R&D chemist for four years, during which time he conducted research on
polyacrylamides. He is now a Senior Scientist in the Production Enhancement product service line at the
Halliburton Technology Center in Pune. His experience includes different applications of polyacrylamides and
corrosion inhibitors for acidizing.

Surachai Kanchiak earned a bachelor's degree in petroleum engineering from Chulalongkorn

University, Thailand, in 2003. He started his oil and gas career that year as the PED Engineer
at Unocal Thailand. He moved on to the Well Services Department the next year and became
involved in planning, overseeing and executing various well intervention and surveillance jobs.          
He then joined the completion department at Chevron Thailand as the Contract Holder for
Coiled Tubing. In 2010, he moved to the Petroleum Engineering department to focus on well
optimization.  

DETAILS

Subject: Oil wells; Corrosion prevention; Hydrochloric acid

Publication title: World Oil; Houston

Pages: n/a

Publication year: 2011

Publication date: Mar 2011

Publisher: Gulf Publishing Co.

Place of publication: Houston

Country of publication: United States, Houston

Publication subject: Petroleum And Gas

ISSN: 00438790

Source type: Trade Journals

Language of publication: English

Document type: News

ProQuest document ID: 861377263

Document URL: https://search.proquest.com/docview/861377263?accountid=12118

Copyright: ( (c) Euromoney Institutional Investor PLC Mar 2011)

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 Last updated: 2017-01-14

Database: ABI/INFORM Collection

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