USMS

020400 Preventive Corrosion Engineering in Crude Oil Production

K.D. Efird, Occidental IntI. E&P Co.

Copyright 1990 Society of Petroleum Engineers

This manuscript was provided to the Society of Petroleum Engineers for distribution
and possible publication in an SPE journal. The material is subject to correction
by the author(s). Permission to copy is restricted to an abstract of not more than
300 words. Write SPE Book Order Dept., Library Technician, P.O. Box 833836,
Richardson, TX 75083-3836 U.S.A. Telex 730989 SPEDAL.
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UNSOLICITED
APR 091990
PREVENTIVE CORROSION ENGINEERING
SPE
PUBUCATIONS IN CRUDE OIL PRODUCTION

by
K. Daniel Efird
Manager, Corrosion Engineering
Occidental International Exploration & Production
Bakersfield, California

SUKKARY

A technique is presented that can be used to accurately predict the produced

water level in crude oil production where accelerated corrosion of steel 1
occurs (defined as the Corrosion Rate Break produced water level), to evaluate
the requirement for corrosion inhibitor treatment, and to evaluate the
requirement for alloys2 as materials of construction. The primary focus is
preventive corrosion engineering in corrosion prediction, material selection
and chemical treatment initiation to minimize the cost of corrosion control
while maximizing its effectiveness. The technique is particularly useful in
making recommendations for new crude oil discoveries where no specific
corrosion data exist. Heavy emphasis is placed on the corrosion of steel,
since steels are the primary materials of construction for crude oil
production systems. Stress corrosion cracking is not included in the
corrosion test procedure, but is addressed in the logic diagram for material
selection. Stress corrosion cracking must be considered based on the well
fluids analysis using standard tests modified to utilize the well fluids.

INTRODUCTION

Successful corrosion engineering of a crude oil production facility for

maximum safety, reliability and economy includes corrosion prediction and

material selection for downhole and surface facilities, specification of

chemical treatment requirements, and determination of when treatment will be

required. To quote from C. Edeleanu (1), "It is simple to recommend that

everything in sight be gold plated .... what is expected from an expert is

1 The word "steel" or "steels" refers to all carbon and low alloy steels
as a group.

2 The word "alloy" or "alloys" refers to all stainless steels and nickel
base alloys as a group.
 SPE 20400
Page 2

guidance on how near the precipice it is safe to go without falling over it."

The problem is to accurately define the location of the precipice, which for

crude oil production is the produced water level where corrosion significantly

increases and the magnitude of the corrosion.

The ability to make accurate predictions about the occurrence of corrosion in

crude oil production systems is very difficult. The acid gas partial

pressures, producing temperature, produced water composition, crude oil

composition, and the amount of produced water all combine to influence the

corrosion characteristics of the production fluids. The inability to

accurately define the production conditions where dangerous levels of

corrosion will occur generally necessitates a very conservative approach to

materials selection due to the consequences of a failure. In crude oil

production where steel corrosion rates increase very rapidly and unexpectedly

as the produced water level increases, corrosion can occur in production

facilities, particularly downhole equipment and tubulars, before the corrosion

monitoring can reliably detect it. This can result in extensive corrosion

damage, requiring replacement of the corroded parts, and has the potential for

dangerous failures.

The onset of accelerated steel corrosion in crude oil production cannot be

reliably predicted by "rule of thumb" produced water levels or by the

"occurrence of free water" in the produced fluids (2). The application of

experimentally derived equations relating temperature and carbon dioxide

partial pressure to the steel corrosion rate are extremely conservative (3-6).

These relationships were primarily derived for gas systems but there have been

attempts to apply these equations to crude oil production. All these

 SPE 2 0 40 0 Page 3

predictive methods are only approximations at best when applied to corrosion

in crude oil production because of the crude oil effect.

The profound effect of the specific crude oil on the corrosion of steel in

sweet (carbon dioxide) production has been demonstrated (2). This work also

confirmed that experiments using only produced water without the crude oil

cannot adequately reproduce steel corrosion in the production system. The

steel corrosion rate without the crude oil present is significantly higher,

therefore excessively conservative, and the magnitude of the steel corrosion

rate at any given produced water level is a highly variable function of the

specific crude oil.

This technique was devised to permit a reasonably accurate prediction of the

produced water level in crude oil production where accelerated corrosion of

steel will become a problem, to determine what chemical treatment will be

required and when it will be required, and to determine when alloys will be

required. All production conditions, compositions and concentrations found in

the field production other than the produced water level must be maintained

for the test program. The results allow good preventive corrosion engineering

to be applied at the initial discovery of a field, during the construction

phase, or early in a field's life.

GENERAL APPROACH TO THE PROBLEM

The approach utilized for new field corrosion testing is given in the logic

diagram of Figure 1. Steels, including corrosion testing of steels, are

appraised before any consideration is given to alloys. This is done because

 SPE 20400 Page 4

the very heavy cost penalty for alloys dictates that steels should generally

be used if technically feasible.

The first step is to obtain field data and samples. No corrosion test can be

any more accurate than the accuracy of the temperature, pressure and

composition data, and the sampling methodology. The well fluids composition,

particularly the gas analysis and produced water analysis must be reasonably

accurate. The crude oil samples for use in the corrosion tests must be

obtained in a manner designed to prevent any contact of the crude oil with

air, i.e., the sample container must be purged with inert gas before crude oil

is introduced into the container, and the crude oil sample must be shipped

under a positive inert gas pressure.

The field data are evaluated as they relate to known corrosion information and

corrosion prevention practices. At this point a decision is made on the

possibility of sulfide stress corrosion cracking, including consideration of

the possibility for future H2 S occurrence even though it is not presently

contained in the produced fluids. If sulfide stress corrosion cracking is a

concern only resistant steels are passed to the corrosion testing phase.

The corrosion tests are conducted to determine the Corrosion Rate Break

produced water level for steel. Generally, only one or two of the steels will

need to be tested, since there is no significant difference in the Corrosion

Rate Break produced water level measured for the various carbon and low alloy

steels commonly used in crude oil service. The Corrosion Rate Break tests are

followed by tests for corrosion inhibitor effectiveness at a produced water

content above the Corrosion Rate Break level. At this point the decision is

made on whether or not steel can be used, based on the corrosion rate data and
 SPE 20400 Page 5

corrosion inhibitor effectiveness coupled with estimates of future produced

water levels during the life of the field.

If steel can be used, the Corrosion Rate Break data are employed to specify:

1. The steels to use for tubulars, wellheads and facilities.

2. The produced water level where the injection of corrosion inhibitor

is required.

3. The corrosion inhibitor to use when the corrosive produced water

level is reached.

If steel cannot be safely used alloys must be evaluated. The consideration of

sulfide stress corrosion cracking must be made for the alloys in the same

manner as for steels. The production environment must also be duplicated in

alloy corrosion tests in the same manner as for steels. Standard corrosion

tests modified to use the production environment are conducted for the alloys

with due consideration given to the probable failure modes, e.g., crevice and

pitting corrosion for stainless steels. On completion of this test sequence,

the alloy or alloys to use for tubulars, wellheads and facilities construction

are specified.

CORROSION TEST PROCEDURE FOR STEEL

Four fundamental corrosion test principles MUST be followed to accurately

determine the produced water level for accelerated corrosion of steel.

 SPE 20400 Page 6

1. Tbe production environment must be duplicated for all corrosion

testing. and its composition other than the relative amounts of the

crude oil and produced water should not be altered in any way.

2. Tbe actual production crude oil must be used for all corrosion

testing. however. artificial produced water may be used.

3. Oxygen must not be allowed to contact the crude oil at any time

before or during corrosion testing.

4. Each individual corrosion test must be completed before the chemistry

of the test environment is changed significantly by the corrosion

process.

The temperature and the partial pressure of the acid gasses (carbon dioxide

and/or hydrogen sulfide) for bottom hole conditions are used for all of the

corrosion tests. The bottom hole temperature and pressure are used since they

generally define the most severe conditions. The corrosion rate measurements

are from either electrochemical linear polarization or weight loss coupons

using 4 coupons per test. The electrochemical linear polarization test

methods used are discussed in detail in Reference 7. The corrosion tests are

conducted in a stirred autoclave in a manner similar to that reported in

Reference 2. A diagram of the autoclave set up is shown in Figure 2.

The test duration is 24 to 36 hours for the electrochemical linear

polarization tests, and 72 to 96 hours for the weight loss coupon tests. The

short test periods are required so each experiment will be complete before the

corrosion process can significantly alter the chemistry of the autoclave

fluids. Previous electrochemical linear polarization tests have shown that

the steady state corrosion rate in sweet crude oil corrosion is generally

reached within 8 hours after exposure begins (2,7). This effect justifies the
 SPE 20400
Page 7

use of the short exposure time corrosion rate as a reasonable measure of the

actual corrosion rate in the crude oil/produced water environment. The use of

4 samples for the weight loss corrosion rate measurements and careful

correction for cleaning weight loss helps overcome some of the variability

inherent in short exposure time weight loss corrosion rate measurements.

The autoclave must be purged with inert gas before the test fluids are

introduced to eliminate oxygen, and all fluid transfer must be made using

inert gas pressure or a vacuum. Oxygen must be completely removed from the

synthetic produced water by inert gas stripping for 24 hours. This is

followed by the addition of catalyzed sodium bisulfite to the produced water

immediately before the test to insure that no oxygen is present.

The extreme measures to insure the complete exclusion of oxygen are taken

because oxygen can react with some crude oils to form organic acids which

could alter the test results. Figure 3 shows the effect of air exposure

(oxygen) on acid compounds present in crude oil C48. Acids in the crude oil

sample were extracted with 0.06 M NaOH, which was then titrated with 0.01 M

Hel. The crude oil sample not exposed to air shows a titration curve that

implies carbonate/bicarbonate as the titrated species, probably originating

from the carbon dioxide in the crude oil reacting with the NaOH. The crude

oil sample that was exposed to air contains 1.5 milliequivalents per liter of

acidic compounds that are not present in the unexposed sample. This

phenomenon does not occur for all crude oils, but it is not possible at this

time to know which crude oils will be affected.

The corrosion tests are conducted at 10% by volume produced water increments

starting with 100% crude oil until a high corrosion rate is obtained, the
 SPE 20400
Page 8

expected produced water limit for the field is reached, or to 90\ produced

water level. If a Corrosion Rate Break (sudden increase in the corrosion rate

between 2 produced water levels) is observed, additional corrosion tests are

conducted at 2\ produced water increments between the two produced water

levels that form the break. Corrosion inhibitors are then evaluated at a

produced water contents 5\ to 10\ above the Corrosion Rate Break level.

The corrosion test results are used to determine if steel can be used, and to

specify the produced water level where chemical treatment must be initiated

and the recommended chemical treatment to use. Utilizing this procedure

materials recommendations can be made during the design stage of a project

before construction of the production facilities begins.

DISCUSSION

The corrosion rate/produced water content curves for crude oils commonly fall

into one of three general behavior categories as shown in Figure 4.

Type 1 behavior is a rapid increase in corrosion rate over a very narrow range

of produced water levels, usually occurring at a produced water level below

20%. This is the most dangerous type of behavior from the corrosion

standpoint, because the increase in corrosion rate is very rapid and the

precise produced water level where this rapid increase occurs is highly crude

oil dependent.

Type 2 behavior is a gradual increase in corrosion rate followed by an

accelerating rate of increase at relatively high produced water levels. This

 SPE 2 0 40 0 Page 9

type is the most difficult for application of the technique because it lacks a

single well defined break in the curve to excessively high corrosion rates.

Type 3 behavior is only a moderate gradual increase in corrosion rate for the

entire range of produced water levels tested. This behavior is observed for

some heavy, asphaltinic or waxy crude oils, and high corrosion rates are only

observed at very high produced water contents.

Following are three examples of the application of the technique to evaluate

the corrosion of steel in new producing wells. Electrochemical linear

polarization tests were used in the first and third examples, while coupon

weight loss tests were used in the second example. The first and second crude

oils are examples of the Type 1 behavior, while the third crude oil is an

example of the Type 2 behavior.

Crude Oil C48 Corrosion Rate Break

Electrochemical linear polarization corrosion tests were conducted for 0.2%

(as received crude oil) to 90% produced water in C48 crude oil. A plot of the

steel corrosion rate variation with the produced water content is given in

Figure 5. The Corrosion Rate Break occurs at approximately 7% produced water,

and corrosion inhibitors were evaluated at a 15% produced water level.

The recommendation to field operations was to begin corrosion inhibitor

injection when the produced water level reached 5% to 7%. At this time the

produced water level for this well has not exceeded 3% and no excessive

corrosion has been encountered.

 SPE 20400 Page 10

Crude Oil PD3 Corrosion Rate Break

Weight loss corrosion tests were conducted for 0.1% (in as received crude oil)

to 10% produced water in PD3 crude oil. A plot of the steel corrosion rate

variation with the produced water content is given in Figure 6. The Corrosion

Rate Break occurs at a very low 2% produced water content, indicating that the

production from this well is extremely corrosive. Corrosion inhibitors were

evaluated at a 10% produced water level.

The recommendation to field operations was to begin corrosion inhibitor

injection when the produced water level reached 1%. The occurrence of

accelerated corrosion at this very low produced water level was subsequently

confirmed, but corrosion inhibitor treatment had been initiated before any

corrosion damage could occur.

Crude Oil CL1 Corrosion Rate Break

Electrochemical linear polarization corrosion tests were conducted for 5% to

90% produced water in CLI crude oil. The plot of the steel corrosion rate

variation with the produced water content is given in Figure 7. The Corrosion

Rate Break produced water level is 30 to 40% produced water for this crude

oil, but the interpretation of this curve for the Corrosion Rate Break is much

more subjective than for the previous examples.

The determination was made that the corrosion monitoring would provide

adequate warning of accelerated steel corrosion for this crude oil so no

refinement in the Corrosion Rate Break produced water level was attempted. A

significant increase in the corrosion rate was detected by the onstream

 SPE 2 0 40 0 Page 11

corrosion monitoring when the produced water level exceeded 40%. Corrosion

inhibitor injection was started and the corrosion is under control.

CONCLUSION

This preventive corrosion engineering technique for determination of the

Corrosion Rate Break produced water level for steel, corrosion inhibitor

treatment requirements, and alloy selection can be used to minimize the cost

of corrosion prevention and control, while at the same time maximizing its

effectiveness. The sequence is straight forward and logical, and produces

results that can be used to accurately define the produced water level where

accelerated corrosion of steel occurs and corrosion inhibitor treatment must

begin, and to make confident, informed determination of the need for alloys in

the production system. The resulting advantages are:

1. The produced wat:er level where accelerat:ed corrosion of st:eel

corrosion in crude oil product:ion will occur can be ident:ified wit:h a

high degree of accuracy and confidence.

2. At: t:he design st:age of new field development: eit:her t:he use of st:eel

or t:he requirement: for alloys is confirmed from corrosion dat:a in t:he

act:ual product:ion environment:.

3. Operat:ing expense is minimized by delaying t:he st:art: of chemical

t:reat:ment: unt:il it: is act:ually necessary.

 SPE 20400
Page 12

4. The danger of faIlures and expense of replacement for corrosion

dBlllBge to facILItIes and downhole equipment and tubulsrs is minimized

by Identifying the produced water level where accelerated corrosion

of steel will begin before dBlllBge actually occurs in the operating

system.
 SPE 20400
Page 13

REFERENCES

1. C. Edeleanu and J. G. Hines, "Conservative Advise can Cost Money,"

Proceedings - 8th International Congress on Hetallic Corrosion, Vol. II,
1981, pp. 1899-1911.

2. K. D. Efird and R. J. Jasinski, "The Effect of the Crude Oil on the

Corrosion of Steel in Crude Oil/Brine Production," Corrosion, Vol. 45,
No.2, February, 1989, pp. 165-171.

3. C. DeYaard and D. E. Milliams, "Carbonic Acid Corrosion of Steel,"

Corrosion, Vol 31, No.5, May, 1975, pp. 177-181.

4. T. Murata, E. Sato and R. Matsuhashi, "Factors Controlling the Corrosion

of Steels in CO2 Saturated Environments," Advances in CO2 Corrosion -
Volume 1, National Association of Corrosion Engineers, 1984, pp. 64-71.

5. J. L. Crolet and M. R. Bonis, "A Tentative Method for Predicting the

Corrosivity of Yells in New CO2 Fields," Advances in COi Corrosion -
Volume 2, National Association of Corrosion Engineers, 1985, pp. 23-38.

6. P. A. Burke, "Synopsis: Recent Progress in the Understanding of CO2

Corrosion," Advances in COi Corrosion - Volume 1, National Association of
Corrosion Engineers, 1984, pp. 3-9.

7. R. J. Jasinski and K. D. Efird, "Electrochemical Corrosion Probe for

Hydrocarbon/yater Mixtures," Corrosion, Vol. 44, No.9, September, 1988,
pp. 658-663.
 SPE 20400 Page 14

FIGURE TITLES

1. The logic diagram for new field corrosion testing to determine the
Corrosion Rate Break produced water level for steel corrosion, corrosion
inhibitor application, and alloy selection.

2. A schematic of the general arrangement of the internal autoclave

components used for the corrosion tests.

3. The effect of exposure to air on the titration curve for acidic compounds
extracted from 200 ml of crude oil C48 with 10 m1 of 0.06 M NaOH using
0.01 M HCl as the titrant.

4. The change in corrosion rate of steel in crude oil/produced water mixtures

with increasing produced water content showing the three general types of
behavior observed.

5. The change in corrosion rate of steel in crude oil C48/produced water

mixtures with increasing produced water content showing a Corrosion Rate
Break at approximately 7% produced water.

6. The change in corrosion rate of steel in crude oil PD3/produced water

mixtures with increasing produced water content showing a Corrosion Rate
Break at approximately 2% produced water.

7. The change in corrosion rate of steel in crude oil PD3/produced water

mixtures with increasing produced water content showing a Corrosion Rate
Break at 30% to 40% produced water.

fn: PREVCOR1.TP
 SPE 20400

OBTAIN FIELD DATA AND NEW FIELD CORROSION

CRUDE OIL SAMPLES
TESTING FOR INHIBITOR
ANALYZE CORROSION DATA AND ALLOY SELECTION
FOR DOWNHOLE CONDITIONS

SELECT STEELS/ALLOYS ON
I - -_ _Y
_E_S ., BASIS OF DATA OR STRESS
CORROSION TESTS FOR
DOWNHOLE CONDITIONS
NO

DETERMINE THE STEEL STEELS en

w
CORROSION RATE BREAK ~
PRODUCED WATER LEVEL PASSING

TEST CORROSION INHIBITORS

AT 5% TO 10% PRODUCED
WATER LEVEL ABOVE THE
CORROSION RATE BREAK

NO

YES NO

LOCALIZED CORROSION
SPECIFY TESTS FOR ALLOYS AT
STEELS FOR USE IN TUBULARS. DOWNHOLE CONDITIONS
WELLHEADS AND FACILITIES.
PRODUCED WATER LEVEL WHERE
CORROSION INHIBITOR IS REO'D. SPECIFY
ALLOY(S} FOR USE IN
CORROSION INHIBITOR TO USE.
TUBULARS. WELLHEADS AND
fn: PCE03.DRW FACILITIES CONSTRUCTION
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 SPE 20400

TITRATION OF CRUDE OIL EXTRACT

200 ml CRUDE OIL + 10 ml 0.06 M NaOH

7 C48 CRUDE OIL

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C48 CRUDE OIL/PRODUCED WATER

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