Products for the petroleum industry

Fig. 1 Schematic illustration of acid corrosion of

carbon steel.
1. Acid corrosion
Acid corrosion is the corrosion of materials in
acidic environments. Many metallic materials
are susceptible to acid corrosion. One of the
most widely used industrial materials, carbon
steel, suffers serious acid corrosion. Corrosion
protection, such as the use of corrosion inhibitors,
is often required for the use of carbon steel in
acidic media.
The mechanism of acid corrosion is straightforward.
In the case of carbon steel, the iron will react with
hydrogen ions to form iron ions and hydrogen gas
(Fig. 1). The reaction is shown below.
Fe + 2H
+
Fe
++
+ H
2
During the process steel is essentially dissolved
away. Weight loss, therefore, is a good measure
of the severity of the acid corrosion.
The corrosion rate of materials in acid is dependent
on parameters such as concentration of pH of
the acidity solution, temperature and the use
of corrosion inhibitors. As acid concentration
i ncreases, the corrosi on rate goes up
correspondingly. At a constant acid concentration,
the corrosion react increases exponentially with
rising temperatures The presence of an acid
corrosion inhibitor will have a profound effect on
the corrosion rate. The addition of 0.1 to 2.0% of
acid corrosion inhibitors can reduce the corrosion
rate up to 95%.
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2. Armohib

acid corrosion
inhibitors from AkzoNobel
Armohib is the trade name for corrosion inhibitors developed by AkzoNobel.
These aliphatic nitrogen inhibitors effectively retard acid corrosion during oil
well acidizing operations, pickling and acid cleaning. AkzoNobel carries two
types of acid corrosion inhibitors: Armohib CI-28 and Armohib CI-31. They are
specially formulated to inhibit corrosion of different acids as listed in Table 1.
Table 1. Application of Armohib corrosion inhibitors in different acids.
Armohib CI-28 Hydrochloric
Hydrochloric-Hydrouoric acid mixtures
Armohib CI-31 Sulfuric
Sulfamic
Citric
Phosphoric
Fig. 2 Schematic illustration of acid corrosion
inhibition by Armohib corrosion inhibitors.
Although the exact mechanism of nitrogen corrosion inhibitors is not fully
understood, it is generally agreed that the positive hydrophilic nitrogen
headgroup absorbs on the metal surface and the aliphatic chains form a
hydrophobic flm, which block the attack of hydrogen ions (Fig. 2). Higher
coverage of the surface with the impervious flm leads to higher acid
corrosion inhibition.
2.1 General properties
of Armohib CI-28 and
Armohib CI-31
The typical properties of Armohib corrosion
inhibitors are listed in Table 2. These inhibitors
are easy to use in the feld. They are available in
liquid form and are soluble in acid. They are non-
staining to metal surfaces and do not precipitate
when standing for a prolonged period of time.
The application of these inhibitors provides low-
cost, dependable protection over a wide range
of temperatures, since only a small quantity of
Armohib inhibitor mixed with the acids will deliver
the desired cleaning effect, while retarding the
acid attack on metals. For example, 0.25%
Armohib CI-28 in 15% hydrochloric acid at 200F
leads to less than 0.022 lb/ft
2
/day corrosion
rate of mild steel. In another example, 0.06%
Armohib CI-31 in 15% sulfuric acid at 200F
leads to less than 0.027 lb/ft
2
/day corrosion rate
of mild steel.
Table 2. Typical properties of Armohib corrosion inhibitors.
Armohib Specifc Pounds per gallons Appearance at 25C Pour point F Flash point F Cloud point F
gravity at 25C
28 0.925 7.69 Amber Liquid 52 90
31 1.042 8.66 Amber Liquid 24 340 28
2.2 Applications of
Armohib CI-28 and
Armohib CI-31
There are three major applications for Armohib
inhibitors: oil well acidizing, acid pickling and plant
cleaning.
Fig. 3 Corrosion
data of mild steel in
hydrochloric acid with
Armohib CI-28.
MILD STEEL IN
HYDROCHLORIC ACID
WITH Armohib CI-28
6 HOURS AT 200F
C
o
r
r
o
s
i
o
n

r
a
t
e

I
b
/
f
t
2
/
d
i
a
Percent inhibitor concentration based on total solution
2.2.1 Oil well acidizing
In the fracturing and acidizing of compact oil
formations, various concentrations of hydrochloric
acid are used to dissolve the undesirable carbonate
deposits of scales, which interfere with the passage
of oil, in tubing or in the formation itself.
The lines and tubing must be protected during this
operation, from corrosive attack by the acid, by
the high temperatures and pressures, and by the
potential for a "sour" environment resulting from
the high hydrogen sulfde and carbon dioxide
contents. Armohib CI-28 used at a concentration
of 0.25%, based on the total hydrochloric acid
solution, is highly recommended for this purpose
(see Fig. 3). It provides effective protection at
temperatures in excess of 230F (110C), for at
least six hours.
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2.2.2 Acid pickling
Pickling is the removal of oxide scales formed
during metal working operations by mineral
acids. Hydrochloric, phosphoric and sulfuric acids
are commonly used. These scales must be
removed without undue acid attack on the base
metal surface.
Armohib

CI-28: Hydrochloric acid is used for
pickling very high carbon alloy steels and for
wire pickling. Hydrogen embrittlement is a major
problem during the pickling of mild steel wire.
The addition of Armohib

CI-28 to the hydrochloric
acid eliminates or reduces embrittlement. The use
of Armohib

CI-28 as an inhibitor, in hydrochloric
acid pickling of steel, has no adverse effect on
the quality of the metal in subsequent hot dip
galvanizing.
Armohib CI-31: Phosphoric acid is used in
the surface preparation of structural steel to
remove mill scale, rust and contaminants, prior
to protective surface coating. Phosphoric acid is
of particular value in pickling operations where the
scale flm is thin, or if the flm is a hydrate oxide
of iron. Sulfuric acid is used extensively in metal
cleaning because of its low cost. In the absence
of inhibitor, up to 80% of the acid may be wasted
in dissolving metal under the scale. The use of
Armohib CI-31 as an inhibitor, regulates the scale
dissolution reactions and minimizes the amount
of surface material that is dissolved.
2.2.3 Plant cleaning
Inhibited acids are used extensively in plant
cleaning; both in pre-commissioning and periodic
planned service cleaning. In all applications,
the use of a corrosion inhibitor is necessary to
maximize the cleaning effect, while minimizing
any unwanted corrosion.
Hydrochloric acid is the acid most often used
for plant cleaning, although sulfamic, sulfuric,
citric and phosphoric acids are also used. The
appropriate Armohib CI-28 or CI-31 product will
serve the corrosion inhibiting needs of any of the
acid applications.
Armohib CI-28 is used to create efficiently
inhibited hydrochloric solutions for hydrochloric
applications for steels such as admiralty, carbon
steels, cast iron, copper and its alloys such as
monel, brass, bronze, cupro-nickel and chrome-
molybdenum.
Sulfamic acid is often used as an alternative
to hydrochloric acid. Sulfamic acid, inhibited
with Armohib CI-31, is used to clean deposits
from 300 and 400 series stainless steels, and
occasional cleaning of aluminum and its alloys.
Armohib corrosion inhibitors may be added to
either dilute or concentrated acid solutions. Never
dilute the Armohib concentrates with water, as
they will separate.
Dilute acid solutions: To obtain the inhibitor
concentrations listed in Table 3, add approximately
the indicated amounts of inhibitors to each 100
gallons of dilute acid solution.
For instructions on handling and storage, please
consult the MSDS sheets for these products.
Table 3. Preparing desired dosage of Armohib corrosion inhibitors

Concentration % total solution .01 .025 .05 .075 .10 .125 .15 .20 .25
Fluid ounces per 100 1.5 3.75 7.5 11.25 15.0 18.75 22.5 30.0 37.5
gallons of total solution
2.3 Applying Armohib CI-28 and Armohib CI-31
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For additional information, samples or assistance please
contact your local sales representative or AkzoNobel's
customer service department at:
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Email: Sc-southamerica@akzonobel.com
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525 W. Van Buren Street
Chicago IL 60607-3823
(800) 906-9977
(312) 544-7000
Email: Csrusa@akzonobel.com
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Singapore Science Park II
#03-03 The Gemini
Singapore 117610
Tel: + 55 6773 8488
Email: Surfacechemistry@ansc.com.sg
Europe, Africa & Middle East
AkzoNobel Surface Chemistry AB
Stenunge All 3
SE-444 85 Stenungsund
Sweden
Tel: + 46 303 8500
Email: Surfactants.Europe@sc.AkzoNobel.com
www.akzonobel.com/surface
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AKZO-3039 AKZO-3034 Acid Corrosion ENGLISH.indd 4 6/6/11 4:48 PM