Binary Corrosion Inhibitors Offer Improved
Corrosion Control
Gene H. Zaid, SPE, and Donald W. Sanders, Jacam Chemicals LLC
Summary
An improvement has been made in anticorrosion chemicals for
oilfield use. A binary corrosion inhibitor that combines an epoxy
resin and an amine curing agent has been patented and field
proven. The proper application of this unique combination of
chemicals forms a bond with the oxide film present on downhole
metal surfaces. The result is a corrosion-inhibitor barrier that is
more tenacious than conventional polar-filming amines, reducing
application frequency and labor costs and, even more important,
downhole failures. The binary corrosion inhibitor is also an improve-
ment over, and is more versatile than, other epoxy-amine products.
Introduction
It is well known that oil and gas wells can be subject to extensive
corrosion. Downhole equipment such as sucker rods, pumps, tub-
ing, and casing are generally made of mild steel that is adversely
affected by production fluids containing carbon dioxide and/or
hydrogen sulfide (H2S) gas, organic acids, or other corrosive ele-
ments. High downhole temperatures and pressures can magnify the
corrosion problem.1,2
A variety of anticorrosion systems has been used in the past.
Most of these are organic inhibitors using nitrogen-based (polar)
amines (also referred to as conventional corrosion inhibitors).
These chemicals work well and are the backbone of many corro-
sion treatment plans, but there are some drawbacks to this treat-
ment method. Varying compositions are required from well to well
for different dispersability and nonemulsification requirements.
Moreover, the useful life of conventional anticorrosion treatments
is very short, lasting a week or less in many systems.1–3 Constant
re-application can be both expensive and inconvenient because
many oil fields are in remote locations.
Epoxy-amine corrosion inhibitors provide improved filming
when compared with conventional polar-amine products, protect-
ing downhole equipment even under extreme temperature and
pressure conditions and in highly corrosive environments.1,2,4
However, there were some improvements to be made with this
system as well. To inhibit agglomeration or clabbering of the
product in the presence of downhole formation water, a high per-
centage of alcohol is needed to be used as a carrier.1,2 Alcohol is
not the best choice in hot climates in which it can quickly evaporate.
The binary corrosion inhibitor is an improvement over both
conventional and other epoxy-amine technologies. The combina-
tion of the particular epoxy resin and amine curing agent chosen
for this system provides improved corrosion protection and ex-
tended treatment intervals when compared with conventional treat-
ments. It is more efficient and versatile than earlier epoxy-amine
formulations because it requires no alcohol to achieve smooth
dispersability and is naturally resistant to freezing.1,2 As of this
writing, the binary corrosion inhibitor has been found to be non-
emulsifying in every crude oil tested from North Dakota to Texas
and from Kansas to California. It is water-dispersible in both fresh
water and high-saline brines.
Components of the Binary Corrosion Inhibitor
A wide variety of different epoxy resin formulations can be used
with good effect in downhole applications, particularly the com-
Copyright © 2005 Society of Petroleum Engineers
This paper (SPE 83481) was first presented at the 2003 SPE Western Regional/AAPG
Pacific Section Joint Meeting, Long Beach, California, U.S.A., 19–24 May, and revised for
publication. Original manuscript received for review 05 November 2003. Revised manu-
script received 15 February 2005. Paper peer approved 16 February 2005.
May 2005 SPE Production & Facilities
mercially available resins that are reaction products of epichloro-
hydrin and bisphenol-A. The epoxy component is preferably dis-
persed in an aromatic hydrocarbon solution, especially those se-
lected from the group consisting of benzene, xylene, toluene,
heavy aromatic naphtha, and mixtures thereof.1,2
The curing agent is selected from the group consisting of the
alkoxylated amines and the imadazolines, and mixtures thereof,
preferably a C1–C18 alkoxylated tallow amine or diamine. The
selected tallow amines and diamines are particularly suitable for
use in oilfield applications. The curing agents are likewise prefer-
ably dispersed in an aromatic hydrocarbon solution, such as those
discussed above in connection with the epoxy resin.1,2
It has been found that the ratio of chemicals should be 3 to 5
parts by volume amine to each part by volume epoxy.
For the chemistry behind this resin-amine system, refer to
the Appendix.
How Binary Corrosion Inhibitors Work
Epoxy-amine compounds, unlike conventional corrosion inhibi-
tors, preferentially adhere to the surface being coated and will
subsequently and spontaneously cure underwater to a tough, ad-
herent, corrosion-resistant film. The chemical will penetrate into
microscopic surface cracks and crevices, displacing water from
them. In a few minutes, any water “sweats out” through the coat-
ing, which binds tenaciously to the areas being treated without an
intervening water layer.5
Conventional anticorrosion chemicals, with their polar charge,
are effective for a time, but by makeup, will eventually lose their
charge and fall away or will be knocked off by fines and erosion.
(See Figs. 1a and 1b for a diagram of the polar amine and how it
films on well tubing.)
When the epoxy and amine are mixed, they have a very strong
attraction to iron oxide or sulfide film on tubulars, rods, and
pumps. A bond, not merely an attraction, is formed. The binary
corrosion inhibitor becomes part of the matrix of the various met-
als, forming an impermeable mesh not easily washed away by
high-velocity fluids or fines. (See Fig. 2.)
How the Binary Corrosion Inhibitor Is Applied
For proper filming and curing, the components of the binary cor-
rosion system must have contact with the downhole metal surfaces
within eight hours of application. Before treating the well, several
pieces of information must be known.
If the well is pounding fluid (i.e., is pumped off), you must
know if fluid added to the annulus is displaced into the reservoir or
remains in the annulus. If fluid overbalances into the reservoir, it
is not recommended that this type of inhibitor be used, because
there is a strong chance that not all of the chemical would return
to the wellhead within eight hours, and proper filming of all down-
hole equipment may not occur.
If the well pounds fluid and injected fluid remains in the an-
nulus, you will need to know how much fluid the well produces per
hour. If the well is not pounding fluid, you will need to learn the
fluid level in the annulus, as well as the amount of fluid produced
per hour. With this information, proper flush amounts can be de-
termined and any required circulation times calculated. Again, it is
important that any binary corrosion chemical added will have a
chance to move down the annulus and come back up to the well-
head within eight hours so that the chemical can properly coat
all surfaces.
The two parts of this coating system can be mixed together at
the wellsite, just before injecting into the well casing, or injected
133
Fig. 1a—Structure of polar amine (polar head with nonpolar
tail).

separately for downhole mixing.1,2,4 The chemicals can be applied

by any convenient means into a production well: by hand, batch-
circulation, extended batch, or with a treating truck. Treating
trucks make the application easier and more efficient because the
two components of the system are injected into the well casing
without stopping well production.1,2 A flush of the annulus is
begun to prewet those surfaces; the chemical is then added with
more flush, followed by a final flush with formation water or
production fluid to ensure that the chemical evenly coats all down-
hole surfaces. If the treater cannot provide enough overflush, then
the well can be circulated for a carefully determined time. The time
needed for circulation can be estimated by a preliminary test in-
volving injection of a fluorescent dye into the circulating-well
fluid and noting the time between injection and appearance of the
dye at the wellhead.1,2 Installation of a circulation timer can sim- Fig. 1b—Filming of polar amines on well tubing. (Polar head is
plify the treating process, minimize labor costs, and keep the well attracted to well tubing. Loss of polar attraction and abrasion by
out of production only as long as necessary for the chemical to coat fines/high-velocity fluids can knock off this type of film.)
all downhole surfaces.
The initial filming process is critical to establishing maximum
film life. Testing has shown that two initial treatments within 1 The current operator took over 1 December 1998, and a deci-
week provide the basis for reduction of subsequent treatment vol- sion was made to switch from conventional corrosion treatment to
umes/frequencies. Further treatment requirements are determined the new binary approach. Treatments for each well are done every
by observation of film life, rather than a ppm requirement, as used 2 weeks using 2 or 3 gal of binary corrosion inhibitor by batch
with conventional inhibitors. treatment with a treater truck. Overflush varies by well, depending
Treatment optimization is achieved through the use of corro- on the static-pumping level. Results were impressive. For the 4
sion coupons, copper-ion displacement tests, iron counts, and elec- years just before using a binary corrosion inhibitor, downhole
trochemical monitoring. Once the optimum treating amount and rod/pump repairs averaged one every 9.6 months. After using the
frequency have been determined, periodic monitoring can ensure new binary corrosion chemical to treat the well, repairs were re-
that the maintenance treatments are providing the desired protection.
Field tests show that the binary system provides excellent cor-
rosion protection, and treatment frequencies are extended 2 to 6
times over conventional inhibitors.

Successful Field-Test Results

Oilfield owners and operators who have changed their corrosion
chemical to the binary approach have seen immediate positive
results. Three case studies are provided below. The first two are
8-year failure histories from two oil fields in Kansas with H2S, or
“sour,” corrosion. Graphs show reductions in well failures after
switching from conventional to binary corrosion inhibitors. The
third study was done with Los Angeles basin wells fighting carbon
dioxide (CO2), or “sweet,” corrosion. Graphs show iron-count
monitoring results after a change to binary corrosion inhibitors
from another epoxy-amine product.

Adell and Northwest Adell. These wells are located in Sheridan

County in northwest Kansas. This field was developed between
1944 and 1952. There are now 16 rod-pumped wells and one
submersible well. Production is from the Lansing Kansas City, a
limestone formation with producing horizons between 3,600 and
3,800 ft. Secondary recovery was initiated in the early 1970s using
Cedar Hill formation water and produced water as injection fluids.
Introduction of the Cedar Hill brine caused a souring of the field
with H2S when injection breakthrough began to occur. Fluid pro-
duction averages 300 to 500 B/D, with oil cuts varying from 1.75
to 5%. The majority of the wells are pounding fluid (i.e., are
pumped off). Current repressuring uses only produced brine. Pre-
vious downhole failures were not only adversely affecting operat-
ing costs, but also were greatly affecting income because the high Fig. 2—Filming of binary corrosion inhibitor. (The binary corro-
static-fluid level required several days of pumping to restore sion inhibitor binds with the tubing, becoming part of its matrix.
oil production. It is resistant to chemicals, fines, and abrasion.)

134 May 2005 SPE Production & Facilities

 Fig. 3—Adell and northwest Adell well failures (*refer to Adell case history for explanation of increased failures for that year).
duced to one every 48 months. Downhole failure expense was thus
reduced by U.S. $11,100 per year.
Fig. 3 illustrates the immediate and sustained reduction in well
failures after the switch in chemical was made. Note that the binary
corrosion chemical was started before the end of the year in 1998
and was already at work reducing failures. The spike in 2000 was
a result of nine rod failures in two wells, which were caused by
loose rod couplings, rather than corrosion. Additionally, a decision
was made that year to replace old tubing when dynamometer test-
ing discovered thread leaks. When tubing was pulled, only one
corrosion pit failure was found (which was external and on the top
sub directly below the surface).
Bindley. This field is located in Hodgeman County in southwest
Kansas, developed in 1972 and 1973. Production is from the Mis-
sissippi dolomite formation at a depth of 4,600 ft. There are 14
rod-pumped wells in the field. Fluid production varies from 25 to
300 B/D. H2S is dissolved in the produced brine at 150 to 500
ppm. All the wells are pumped off.
This was another test site for the binary corrosion inhibitor.
Low fluid-production wells are now treated once monthly with 1
gallon of binary corrosion inhibitor. Higher fluid-production wells
Fig. 4—Bindley well failures (reductions in well failures after the switch from a conventional polar-amine corrosion inhibitor to the
binary corrosion inhibitor).
May 2005 SPE Production & Facilities
are treated with 1.5 gallons once every 2 weeks. Chemical is added
by batch treatment with a treater truck with 4-bbl overflush. Again,
an 8-year study was done. Total downhole failures were reduced
by 84%. There were two pump repairs in the 4 years before the
binary treatment and none in the 4 years since. Pumps on these
wells are always repaired when tubing is pulled. Downhole failure
expense has thus been reduced by U.S. $66,600 over the 4 years,
or U.S. $16,650 per year.
Fig. 4 also shows dramatic reductions in well failures. Again,
the binary corrosion chemical was started on 1 December 1998,
which helped lower repairs for that year somewhat.
Los Angeles Basin. The wells in this study produce from the
Alamitos and Brown zones, with depths ranging from 2,500 to
4,700 ft. Total fluid production averages between 400 and 750 B/D
and oil percentages vary from 2.3 to 7.6%.
Approximately 80 wells previously treated with another epoxy-
amine product were selected for preliminary testing of the binary
corrosion inhibitor. Iron-count monitoring (a proven method of
confirming corrosion inhibition in CO2 systems) was used to track
corrosion control for these wells. As a result of successful testing,
the majority of the operator’s 145 producing wells were switched
135
Fig. 5—Monthly iron-count monitoring of three Los Angeles basin wells (reductions in well failures after the switch from another
epoxy-amine corrosion inhibitor to the binary corrosion inhibitor).

to the binary corrosion inhibitor, including 30 wells previously
treated with conventional corrosion chemicals.
The wells were initially treated with binary corrosion inhibitor
once per week by batch application with a treater truck. After close
analysis of the produced water, it was determined that several of
the wells were experiencing high abrasion/erosion corrosion, and
for these wells, treatment was increased to twice per week. For the
majority of the wells, iron levels dropped to those naturally pro-
duced by the formation, clearly indicating improved corrosion con-
trol. Representative iron testing results are shown in Figs. 5 and 6.
Fig. 5 displays the iron counts of three wells treated with an-
other epoxy-amine product and downward trends in iron levels
observed after changing to the binary corrosion inhibitor in March
2002 (dotted vertical line). Sharp drops in iron after each treatment
are also evident. Significant reductions of iron achieved in all three
wells matched desired goals set by the operator.

Fig. 6—Daily iron-count monitoring of three Los Angeles basin wells.

136 May 2005 SPE Production & Facilities

 Fig. 6 tracks the results of the twice-weekly treatment test on
three high-abrasion wells. Each well was treated on 30 December
2002, 3 January 2003, 6 January 2003, and 10 January 2003. Trend
lines illustrate the drop in iron levels in the produced water im-
mediately following treatment and the increased iron levels return-
ing as the film layer was worn off through abrasion.
Particularly in light of perceived decreased frequency of well
failures, the operator of these wells remains pleased with the im-
provement in overall corrosion control achieved after the switch to
a binary corrosion inhibitor.
Conclusions
Binary corrosion inhibitors offer improved corrosion control over
polar amine chemicals and other epoxy-amine technologies.
Downhole surfaces treated with binary corrosion inhibitors are
better protected against the various factors that work to corrode
them. The binary anticorrosion product is applied less often, re-
ducing chemical and labor costs. And even more importantly, by
protecting the tubulars and rods from failure, the oil and gas own-
ers and operators net additional profits by reducing downtime and
high replacement and repair costs.
Acknowledgments
The authors wish to thank D.J. Brownlee Foster, Special Projects,
Jacam Chemicals LLC; J.K. Marshall, Engineer, Jacam Chemicals
LLC; B.A. Wolf, Lab Manager, Jacam Chemicals LLC; D. Slater,
Vice President, Signal Hill Petroleum; R. Bates, Senior Petroleum
Engineer, Signal Hill Petroleum; and S. McDaniel, Operations
Foreman, Signal Hill Petroleum.
References
1. Zaid, G.H.: “Epoxy Corrosion Inhibition Systems Including Ethoxy-
lated Curing Agents,” U.S. Patent No. 5,945,164 (1999).
2. Zaid, G.H.: “Epoxy Corrosion Inhibition Systems Including Ethoxy-
lated Curing Agents,” U.S. Patent No. 5,936,059 (1999).
3. Zaid, G.H.: “Dispersed Oil Soluble Corrosion Inhibitor and Water
Soluble Phosphonate Scale Inhibitor Composition,” U.S. Patent No.
4,713,184 (1987).
4. Wu, Y.: “Composition and Method for Corrosion Inhibition,” U.S.
Patent No. 4,526,813 (1985).
5. Cummings, L.O.: “Method for Coating Wet Surfaces of Surfaces Im-
mersed in Water,” U.S. Patent No. 4,022,946 (1977).
6. Bull. SC:67-01, EPON Resin Structural Reference Manual, Resolution
Performance Products (2001) Chap. 3, 3-1–3-2.
Appendix
Binary Chemistry.6 Binary resins are characterized by the pres-
ence of epoxide functionality:
The most widely used binary resins are the reaction products of
epichlorohydrin and bisphenol-A. The molecular weight of the
resin is a function of the ratio of the reactants. An idealized struc-
ture appears below:
Typical liquid resins used have n values of 0 to 1.
In addition to the bisphenol-A-based resins, other types of ep-
oxy resins that can be used include the aliphatic and cy-
May 2005 SPE Production & Facilities
cloaliphatic-epoxy resins, bisphenol-F-based resins, glycidated no-
volacs, and tetraglycidyl ether of tetraphenylolethane. The latter
two types of materials, having a high aromatic ring content com-
bined with polyfunctionality, provide increased thermal stability
for high-temperature applications.
Binary resins can be cured by a large variety of chemical com-
pounds. For the purposes of oilfield application, only the two most
important classes of curing agents will be discussed.
Primary and Secondary Amines. These classes of materials
are those most widely used to cure resins. The reaction between
the oxirane group on an epoxy resin and an amine is illus-
trated below:
The remaining amine hydrogen may also react as follows:
In this fashion, the use of a compound containing a plurality of
primary, or primary and secondary, amine groups as a curing agent
for a diepoxide will result in a 3D, crosslinked polymer network.
The stoichiometric quantity of amine to be used to cure an
epoxy resin is easily calculated from the molecular weight of the
amine, the number of active hydrogens in the amine, and the
weight per epoxide or equivalent weight of the epoxy resin, as
shown below:
冉 冊
Molecular weight of amine
Number of available hydrogen
× 100
Weight per epoxide
冉Parts
with 100 parts by weight of resins 冊
by weight of amine to be used
=
SI Metric Conversion Factors
bbl × 1.589 873 E-01 ⳱ m3
B/D × 1.589 873 E–01 ⳱ m3/d
ft × 3.048* E-01 ⳱ m
*Conversion factor is exact.
Gene H. Zaid is Founder, President, and CEO of Jacam Chemi-
cals LLC, Sterling, Kansas, U.S.A. (e-mail: ghz@jacam.com.). Be-
fore he founded Jacam 23 years ago, he spent 5 years as a
chemist in the salt industry, 3 years as a research chemist at
Farmland Industries, and 2 years as a process control chemist
at Boeing Aircraft Co. Zaid holds 30 patents devoted to the oil
and gas production industry, a BA degree in chemistry and
mathematics from Kansas Wesleyan U., an MS degree in
chemistry from Wichita State U., and an MBA degree from Cali-
fornia Coast U. Donald W. Sanders is Vice President of Jacam
Chemicals LLC, Sterling, Kansas, U.S.A. (dsanders31@cox.net)
He has been Vice President at Jacam for the last 12 years.
Before that, he spent 35 years in the oil and gas industry in sales
management and product development, 11 years with Nalco
Chemical as Kansas District Manager, 12 years with Baker Per-
formance Chemicals, most recently as midcontinent Regional
Manager. Sanders holds one patent devoted to the oil and
gas production industry and a BA degree in marketing and
finance from the U. of Texas.
137