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(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual Property


Organization
International Bureau
(10) International Publication Number
(43) International Publication Date WO 2014/178738 Al
6 November 2014 (06.11.2014) PO PCT

(51) International Patent Classification: ANSKI, Leszek; ul. Zawieyskiego 4/2, PL-30-619 Krakow
C09K 8/54 (2006.01) C23F 11/14 (2006.01) (PL). SKRET, Iwona; ul. Chalupnika 4/41, PL-3 1-464
Krakow (PL). PTAK, Stefan; ul. Wronskich 79, PL-38-
(21) International Application Number:
300 Gorlice (PL). ZEGARMISTRZ, Ewa; ul. Staszica
PCT/PL20 14/000048
5/2, Krakow (PL). SOCHA, Mieczyslaw; ul. Jerz-
(22) International Filing Date: manowskiego 12/49, PL-30-036 Krakow (PL).
5 May 2014 (05.05.2014) PACKOWSKI, Zbigniew; ul. Wawrzynca Sikory 12, PL-
09-410 Plock (PL).
(25) Filing Language: English
(74) Agents: DOSKOCZYNSKA - GROYECKA, Anna et
(26) Publication Language: English al.; Kancelaria Rzecznika Patentowego, ul. Zaleskiego 9/4,
(30) Priority Data: PL-3 1-525 Krakow (PL).
P.403749 2 May 2013 (02.05.2013) (81) Designated States (unless otherwise indicated, for every
P.40375 1 2 May 2013 (02.05.2013) kind of national protection available): AE, AG, AL, AM,
(71) Applicant: INSTYTUT NAFTY I GAZU - PANST- AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY,
WOWY INSTYTUT BADAWCZY [PL/PL]; Ul. Lubicz BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM,
25A, 3 1-503 Krakow (PL). DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,
HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR,
(72) Inventors: GAZDZIK, Barbara; ul. Praska 46, PL-30- KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME,
329 Krakow (PL). MAZELA, Wojciech; ul. Komandosow MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ,
15/5, PL-30-334 Krakow (PL). PAJDA, Michal; ul. Try- OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA,
buny Ludow 44/8, PL-30-660 Krakow (PL). ZIEMI- SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM,

[Continued on nextpage]

(54) Title: WATER-SOLUBLE CORROSION INHIBITOR FOR PROTECTION OF LIFTING CASINGS AND NATURAL GAS
PIPELINES AS WELL AS THE METHOD OF ITS PRODUCTION.
(57) Abstract: The water-soluble corrosion inhibitor for protection of lifting cas
ings and natural gas pipelines contains: - component a) obtained through neutral
ization from 0 . 1 to 50 % by weight, of the new mixture of modified imidazoline
derivatives, which constitutes a mixture of substances of general formulas (1) and
(2), wherein Ri: C 12 -C 22 wherein R 2:C 2 -Ci 2 with the possible addition of a product
of general formula ( ) wherein R : C 12 -C 24 with an aliphatic and/or aromatic
monocarboxylic acid containing from 1 to 7 carbon atoms per molecule, - com
ponent b) that is oxyethylenated fatty amines containing from 2 to 20 ethoxyl
groups per molecule - component c) that is an alkalizing agent - optional compon
ent d) that is an aliphatic polyol - component e) that is an aliphatic alcohol con
taining from 1 to 6 carbon atoms per molecule, optionally with the addition of
water - component f that is an anti-foaming agent.

( ')

o
o
w o 2014/178738 Ai II II I II III Iill I I 11 III llll M ill II I II
TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK,
ZW. SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ,
GW, KM, ML, MR, NE, SN, TD, TG).
(84) Designated States (unless otherwise indicated, for every
kind of regional protection available): ARIPO (BW, GH, Published:
GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ,
— with international search report (Art. 21(3))
UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ,
TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, — with amended claims and statement (Art. 19(1))
EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU,
TITLE:

Water-soluble corrosion inhibitor for protection of lifting casings and natural gas
pipelines as well as the method of its production.

TECHNICAL FIELD:

The invention relates to a water-soluble corrosion inhibitor for protection of lifting


casings and natural gas pipelines as well as to the method of its production.

BACKGROUND ART:

The phenomenon of corrosion is a serious problem in the natural gas extraction


industry and is the result of chemical or electrochemical reactions of metal elements with
the environment.

More than one type of corrosion occurs in gas wells. Drilling fluids are usually
aqueous saline solutions that perform the role of an electrolyte. Produced water, which is
present during the extraction of natural gas, also contains inorganic salts such as chlorides
(sodium, potassium, magnesium), sulfates (sodium, potassium, magnesium), and
carbonates. Electrochemical corrosion occurs readily in aqueous systems containing salts.
It is caused by the action of galvanic cells forming between the passivated metal surface
and a surface that does not possess such a layer. The effect of electrochemical corrosion is
mainly pitting corrosion on the surfaces of lifting casings and pipelines as well as on
operational equipment. The most damage to pipe and casing surfaces occurs in saline
solutions with concentrations of 7 - 13 %.

Large corrosion damage is caused by the presence of carbon dioxide in the drilled
deposit. A characteristic trait of the corrosion resulting from the presence of carbon dioxide
in extracted gas is the presence of smooth well edges. Corrosion caused by the presence of
carbon dioxide in gas wells is often called "neutral" corrosion. Carbon dioxide, when
dissolved in water, forms H2C0 3, which then reacts with iron to form iron carbonate
FeC0 3, and hydrogen gas H2 is also formed. When carbon dioxide dissolves in water, it
also reduces the pH of water, thus causing an increase of the corrosion rate.
Corrosion resulting from the presence of hydrogen sulfide is just as serious and is
referred to as "sour" corrosion. Hydrogen sulfide content in extracted gas generally
amounts to from one to a dozens of percent, but some gas deposits contain up to several
dozen percent of hydrogen sulfide. Hydrogen sulfide causes more aggressive corrosion
than carbon dioxide. Similarly to carbon dioxide, hydrogen sulfide dissolves in water,
reducing pH. As a result of the reaction of hydrogen sulfide with iron, iron sulfide FeS and
hydrogen gas ¾ are formed. Iron sulfide forms a coating on metal surfaces, and during the
first phase, it inhibits "sour" corrosion, however even slight damage to this coating causes
intensive corrosion. "Sour" corrosion causes pits to form and is also often accompanied by
cracking of metal coatings caused by the production of hydrogen. Some hydrogen
penetrates into steel and becomes the cause of blistering, cracking, and so-called hydrogen
embrittlement.

Corrosion processes in gas wells are intensified by Desulfovibrio Desulfuricans


sulfate-reducing bacteria. These bacteria are most active when under the surface of scales
formed as a result of sediment deposition.

The rate of corrosion induced by carbon dioxide and hydrogen sulfide increases as
the oxygen content in the system increases. Oxygen penetrates into drilling fluids when
they pass through machinery servicing wells and tanks. The rate of corrosion is also
dependent on temperature; the greater it is, the greater the corrosion rate, which reaches its
maximum at a temperature of approx. 70°C. In wells that are not protected with corrosion
inhibitors, it may even reach up to several mm/year.

Gas is saturated with water vapor in deposit conditions as a result of long-term


contact of natural gas with formation water. The amount of vapor in gas depends on
temperature, pressure, and salt content in the water. The amount of water vapor in gas rises
during exploitation of the deposit, and the older it is, the greater the amount of water vapor
in the gas. Due to pressure reduction in gas pipelines, water is released, and its presence
accelerates corrosion.

The effects of corrosion processes are: reduction of the thickness of lifting casing
walls and pipeline walls, deep pitting that may lead to leaks, and severe reduction of their
strength properties.
In order to prevent corrosion in gas wells, corrosion inhibitors reducing the
corrosive action of extracted natural gas on steel parts of extraction equipment and
pipelines are used. Liquid corrosion inhibitors of varying chemical nature are used as
corrosion inhibitors: most frequently quaternary ammonium salts, imidazoline derivatives,
fatty acid salts, and protective gaseous inhibitors, usually amines. In order to be effective,
an implemented corrosion inhibitor should be dissolved in water for the purpose of
neutralizing the corrosive action of the salts and acidic gases dissolved in the water.

The water-soluble corrosion inhibitor for protection of natural gas lifting casings
and pipelines provides corrosion protection against substances such as: hydrogen sulfide
and carbon dioxide present in the extracted gas, chlorides present in the formation water
and drilling fluids, as well as the oxygen present in the water.

Patents US 3629104 and US 3758493 describe water-soluble corrosion inhibitors


containing a carboxylic acid of an imidazoline derivative produced by condensation of
dimerized fatty acids with diethylenetriamine.
US Patent 5759485 describes the method of producing the corrosion inhibitor by
neutralization of C2 tricarboxylic acids and subsequent addition of imidazoline or
amidoamine.
Patent application WO 2003/054251 contains a description of the good anti-
corrosion properties of ethoxylated fatty alkyl amines, particularly ethoxylated alkyl ether
amines.
Patent descriptions PL 61535 and PL 85729 disclose that imidazoline inhibitors are
produced in a condensation reaction of diethylenetriamine with fatty acids or naphthenic
acids.
Patent descriptions PL 135655 and PL 175452 present production of an inhibitor
with increased activity, which is a result of condensation of diethylenetriamine with fatty
acids and is then modified using urotropine introduced during the final phase of the
condensation reaction.
According to patent PL 182943, the water-soluble corrosion inhibitor contains a salt
of an imidazoline derivative that constitutes the product of condensation of fatty acids with
diethylenetriamine and urotropine or formaldehyde as well as low molecular carboxylic
acids.
Patent application US 2004/0087448 recommends the use of the product of
condensation of unsaturated fatty acids dimmers, containing 1 or 2 double bonds, and
diethylenetriamine .
In turn, US Patent 6695897 contains a description of a method of producing
amidoamine by condensation of N-ethylethylenediamine and fatty acid. The product of the
reaction after solubilization with acetic acid may perform the role of a water-soluble
corrosion inhibitor.
Patent description US 7057050 presents a method for producing a water-soluble
corrosion inhibitor. The product of this reaction is N-propyl-2-heptadecenyl imidazoline.
The obtained product is transformed to a water-soluble form using acrylic acid.
Patent application WO 2006/078723 contains a description of a method of
producing micro-emulsions containing imidazoline derivatives and amidoamines produced
in the presence of oleic acid. The micro-emulsion also contains ethoxylated nonylphenols
and acetic acid.
Patent literature contains descriptions of condensation of diethylenetriamine with
fatty acids containing from 12 to 24 carbon atoms per molecule, with ratio of
diethylenetriamine to fatty acids equal to 1:0.5 - 1.0. Examples of such condensation are
known from, among others, American patent descriptions US 2267965, US 2355837, and
Polish patent description PL 61535.

Patent description US 5322630 discloses an imidazoline corrosion inhibitor that is


the product of the reaction of unsaturated monocarboxylic acids with fatty amines,
aminoamides, or fatty imidazole-amines.

Patent description RU 2394941 describes a mixture of imidazoline derivatives


modified with aldimines or Schiff bases. According to this patent, the imidazoline
derivative is the product of the reaction of polyamines with oleic acid or monocarboxylic
acids. The imidazoline derivative is then cyanoethylated with nitriles, acrylic acid, or
subjected to oxyalkylation.

The water-soluble corrosion inhibitor, produced by neutralization of tricarboxylic


acid with arninoethylethanolamine and subsequently with an imidazoline derivative,
amidoamine derivative, or a mixture of the two, is presented in patent description US
5759485.

Patent description GB 2340505 presents a method for producing imidazoline


derivatives in the process of condensation of tall oil fatty acids with
aminoethylethanolamine. The inhibitor is characterized by good anti-corrosion properties,
and by forming complexes with mercaptanes, it neutralizes the odour of sulfur compounds.

US Patent 5723061 and US patent application 2007/0152191 describe compositions


with components including salts produced in a reaction of C10 -Cj2 dicarboxylic acids with
polyamines.

Corrosion inhibitors that include bis-amides are described in American patents. A


bis-amide that is the product of the reaction of polyamines with fatty acid dimers is
described in US Patent 4614600, and the product of the reaction of polyamines with
dicarboxylic acids is described in US Patent 4344861.

Patent application WO 2003/054251 discloses the anti-corrosion properties of


ethoxylated fatty alkyl amines, particularly ethoxylated alkyl ether amines.

Patent application US 2009/181678 recommends the use of the product of


condensation of C 1 unsaturated fatty acids dimers (containing 1 or 2 double bonds) with
diethylenetriamine.

Patent application US 2007/0261842 contains a description of the corrosion


inhibition process in pipelines transporting crude oil/natural gas through the application of
at least one amine that boils within a temperature range of 105 - 130°C or at least one
amine selected from among mono-, di-, and tri-alkylpyridine, 3-methoxypropylamine
(MOPA), ethyldiisopropylamine (EDIPA); the composition of the inhibitor may
additionally contain at least one imidazoline or its derivative and/or phosphorus esters
and/or thioacids.

Many available corrosion inhibitors for protection of natural gas lifting casings and
pipelines are insufficiently effective and require high doses in order to provide corrosion
protection. It has been accepted that the level of corrosion protection at a dosage of 100 mg
of corrosion inhibitor per 1 kg of corrosive medium should be greater than 80% according
to standard ASTM NACE 1D182.

Most offered corrosion inhibitors destined for application in natural gas wells are
based on quaternary ammonium salts. These types of compounds are totally soluble in
water, which is why they are readily applied by producers. The best corrosion inhibitors
are those that are very well soluble in water while leaving a layer of the corrosion inhibitor
on metal surfaces. A corrosion inhibitor should provide protection for a
pipeline/installation for at least 24 h from an emergency stoppage of the dosing pump. A
drawback of corrosion inhibitors based on quaternary ammonium salts is that they have
much lower anti-corrosion properties than inhibitors containing imidazoline derivatives,
specifically, they do not provide sufficient protection against pitting corrosion.

Many available corrosion inhibitors for protection of natural gas bore-holes and
pipelines are insufficiently effective and require high doses in order to provide corrosion
protection. Many of them form an inhomogenous liquid after being mixed with formation
water, with release of sediments and precipitation of a part of the inhibitor. This results in
insufficient corrosion protection and may also be the cause of the occurrence of dangerous
pitting corrosion.
An additional inconvenience of available inhibitors is their tendency to form
emulsions with formation water. Others exhibit significant foaming tendencies, and the
presence of foam disrupts the operation of gas well equipment.
The purpose of the invention was to develop a water-soluble corrosion inhibitor for
protection of natural gas lifting casings and pipelines that would provide much better anti-
corrosion properties than current corrosion inhibitors.

SUMMARY OF THE INVENTION:

The present invention relates to a water-soluble corrosion inhibitor for protection of


lifting casings and natural gas pipelines as well as to the method of its production.

One aspect of the invention is to provide a water-soluble corrosion inhibitor for


protection of lifting casings and natural gas pipelines.
It was stated that a composition containing the following components exhibits good
anti-corrosion properties, sufficient for protection of natural gas extraction equipment and
gas pipelines:
- component a) in an amount from 0.15 to 75 % by weight, preferably from 1.5 to 35 % by
weight, obtained by neutralization from 0.1 to 50 % by weight, preferably from 1 to 30 %
by weight, of the new mixture of modified imidazoline derivatives, which is a product of
condensation of diethylenetriamine with fatty acids containing from 1 to 22 carbon atoms
per molecule and aliphatic dicarboxylic acids containing from 2 to 12 carbon atoms per
molecule, which constitutes a mixture of compounds of general formulae (1) and (2),

wherein : C 2 -C2 2 (1)

with the optional addition of from 0.05 to 20 % by weight of the known product of
condensation of diethylenetriamine with fatty acids containing from 12 to 24 carbon atoms
per molecule, produced by a known method at a temperature of 180-280°C, preferably
220-260°C, of general formula (1')

wherein R 3 : C i2-C24 ( )

with an aliphatic and/or aromatic monocarboxylic acid containing from 1 to 7 carbon


atoms per molecule, used in an amount from 0.05 to 25 % by weight, in which
neutralization the mass ratio of the mixture of compounds of general formulae (1), (2),
and optionally ( ) to monocarboxylic acid is 1: 0.15 - 0.70, with obtaining of the final
product, which is a mixture of compounds of general formulae (5), (6), and optionally (5')

wherein (5)
R4: H, C!-C , aromatic radical (C H6)

wherein R3: C12 -C2 4 (5 ' )


R4: H, CrC , aromatic radical (C H )
- component b) that is oxyethylenated fatty amines containing from 14 to 22 carbon atoms
per molecule and from 2 to 20, preferably from 3 to 15, ethoxyl groups per molecule, in an
amount from 0.01 to 10 % by weight;
- component c) that is alkalizing agent in an amount from 0.06 to 25 % by weight,
preferably from 1 to 20 % by weight;
- optional component d) that is aliphatic polyols in an amount from 0.04 to 50 % by
weight;
- component e) that is aliphatic alcohols containing from 1 to 6 carbon atoms per molecule,
optionally with the addition of water, in an amount from 15 to 99.7 % by weight
and
- component f that is anti-foaming agent in an amount from 0.01 to 2 % by weight.

Another aspect of the present invention is to provide the method of producing the
water-soluble corrosion inhibitor for protection of lifting casings and natural gas pipelines,
which consists of the following stages:
I) production of component a), that is neutralization carried out at room temperature
in a reaction medium containing component e), that is aliphatic alcohols containing from 1
to 6 carbon atoms per molecule, optionally with the addition of water, in an amount from
15 to 99.7 % by weight, of the new mixture of modified imidazoline derivatives that is the
product of condensation of diethylenetriamine with fatty acids containing from 12 to 22
carbon atoms per molecule and aliphatic dicarboxylic acids containing from 2 to 12 carbon
atoms per molecule, constituting a mixture of compounds of general formulae (1) and (2),

wherein \ C 2 -C22 (1)


H2N NH2
wherein R2 : C2-C 2 (2)

used in an amount from 0.1 to 50 % by weight, preferably from 1 to 30 % by weight, with


the optional addition of 0.05 to 20 % by weight of the known product of condensation of
diethylenetriamine with fatty acids containing from 12 to 24 carbon atoms per molecule,
produced by a known method at a temperature of 180-280°C, preferably 220-260°C, of
general formula ( ),

wherein R 3: C 12 -C 24 (

with an aliphatic and/or aromatic monocarboxylic acid containing from 1 to 7 carbon


atoms per molecule, used in an amount from 0.05 to 25 % by weight, where the mass ratio
of the mixture of compounds of general formulae (1), (2), and optionally ( ) to
monocarboxylic acid is 1 : 0.15 - 0.70, with obtaining of the final product, which is a
mixture of compounds of general formulae (5), (6), and optionally (5'),

wherein R C 12 -C22 ( 5)
R4 : H, CrC 6, aromatic radical (C 6H6)
wherein R3 : C 12 -C24 (5)
H, C C6, aromatic radical (C H )

II) introduction to component a), in an amount from 0.15 to 75% by weight, preferably
from 1.5 to 35% by weight, and to the mentioned component e), of further inhibitor
components:
component b), that is oxyethylenated fatty amines containing from 14 to 22 carbon atoms
and from 2 to 20, preferably from 3 to 15, ethoxyl groups per molecule, in an amount from
0.01 to 10% by weight;
component c), which is an alkalizing agent in an amount from 0.06 to 25% by weight,
preferably from 1 to 20% by weight;
optionally component d), that is aliphatic polyols in an amount from 0.04 to 50% by
weight,
and finally, component f), which is an anti-foaming agent in an amount from 0.01 to 2% by
weight.
DESCRIPTION OF THE PREFERRED EMBODIMENTS:

It was unexpectedly noted that the application of a new mixture of modified


imidazoline derivatives with better anti-corrosion properties, possibly with addition of
known product of condensation of diethylenetrianine with fatty acids, neutralized with an
aliphatic and/or aromatic monocarboxylic acid to form a salt, and an active surfactant from
the group of oxyethylenated, hydrogenated tall oil amines with a double function:
corrosion inhibitor and dispersant, in combination with a volatile amine, an anti-foaming
agent, optionally with addition of aliphatic polyols, dissolved in an alcohol solvent,
optionally with addition of water, resulted in obtaining of a corrosion inhibitor with
increased anti-corrosion properties as compared to corrosion inhibitors containing
conventional imidazoline derivatives.

In this invention, a new mixture of modified imidazoline derivatives of general


formulae (1) and (2) is used,

wherein R : Ci2-C2 2

wherein R2 : C2-C 12
which is obtainable in such a way, that condensation of diethylenetriamine is performed
with fatty acids containing 12-22 carbon atoms per molecule and aliphatic dicarboxylic
acids containing 2-12 carbon atoms per molecule, where the molar ratio of
diethylenetriamine to fatty acids and to aliphatic dicarboxylic acids is 1: 0,5-0,99: 0.01-0.5,
at a temperature of at least 140°C, preferably 150°C, with the formation of an aminoamide
mixture of general formulae (3) and (4),

wherein R : C 1 -C2 (3)

with acid number < 10 mg KOH/g,

and next, the temperature is raised to above 180 °C, preferably to 220 °C, and the
condensation reaction is performed further until a mixture of compounds of general
formulae (1) and (2) is obtained

wherein R : C12 -C22 (1)


with acid number < 1 mg KOH/g.

This new mixture of modified imidazoline derivatives forms an exceptionally


durable layer on metal surfaces that protects against corrosion. The application of a volatile
amine as one of the inhibitor's components, completes its anti-corrosion action in the
gaseous phase.
Many available corrosion inhibitors for protection of natural gas wells and pipelines
contain dispersants derived from nonylphenol among their components. Phenol groups are
particularly harmful to the natural environment due to their very low biodegradation.
According to this invention, the application of a surfactant from the group of
oxyethylenated, hydrogenated, tall oil amines in the composition of this corrosion
inhibitor, which have a very high degree of biodegradation, had a favorable impact on its
biocompatibility.
There can be many embodiments of the invention depending on variants of its components
and the ways they are combined. The preferred embodiments of the invention concerning
components a), e), d), c) and f are listed below.

In the preferred embodiment of the invention, the corrosion inhibitor contains as


component a) a product formed by neutralization with acetic acid and/or benzoic acid of
the following imidazoline derivatives:
i) the new mixture of modified imidazoline derivatives, which is condensation product of
diethylenetriamine with fatty acids containing 12-22 carbon atoms per molecule and
aliphatic dicarboxylic acids containing 6-10 carbon atoms per molecule, where the molar
ratio of diethylenetriamine to fatty acids and to aliphatic dicarboxylic acids is 1: 0,5-0,99:
0.01-0.5, at a temperature of at least 140°C, preferably 150°C, with the formation of an
aminoamide mixture of general formulae (3) and (4),

with acid number < 10 g KOH/g,

and next, the temperature is raised to above 180 °C, preferably to 220 °C, and the
condensation reaction is performed further until a mixture of compounds of general
formulae (1) and (2) is obtained

wherein C 12 -C22 (1)


wherein R2 : C 6-C 10 (2)

with acid number < 1 mg KOH/g,

ii) optionally added, the known product of condensation of diethylenetriamine with fatty
acids.
In the preferred embodiment of the invention, the corrosion inhibitor contains methanol,
isopropanol, ethanol, or their mixtures as component e).
In the preferred embodiment of the invention, the corrosion inhibitor contains ethylene
glycol, glycerin, propylene glycol, dipropylene glycol, tripropylene glycol, or their
mixtures as component d).
In the preferred embodiment of the invention, the corrosion inhibitor contains 3-
methoxypropylamine, 2-aminoethanol (monoethanolamine), diethylamine, or their mixture
as component c).
In the preferred embodiment of the invention, the corrosion inhibitor contains siloxane
derivative, more preferably branched siloxane polymers as component f).
The composition of the corrosion inhibitor according to the invention has been given in
percentages by weight calculated in reference to the total mass of the inhibitor.

In the preferred embodiment of the invention, concerning the method of production


of water-soluble corrosion inhibitor for protection of lifting casings and natural gas
pipelines, neutralization with glacial acetic acid is carried out of the following imidazoline
derivatives :

i) new mixture of modified imidazoline derivatives, which is condensation product of


diethylenetriamine with fatty acids containing 12-22 carbon atoms per molecule and
aliphatic dicarboxylic acids containing 6-10 carbon atoms per molecule, in which
condensation the molar ratio of diethylenetriamine to fatty acids and to aliphatic
dicarboxylic acids is 1 : 0,5-0,99: 0.01-0.5, at a temperature of at least 140°C, preferably
150°C, with the formation of an aminoamide mixture of general formulae (3) and (4),

with acid number < 10 mg OH/g,

after which the temperature of the reaction is raised to above 180 °C, preferably to 220 °C,
and as a result of the reaction, a mixture of compounds of general formulae (1) and (2) is
obtained

wherein Ri: C 12 -C22 (1)


with acid number < 1 mg KOH/g,

ii) optionally added the known product of condensation of diethylenetriamine with fatty
acids.

The percentages of components used to produce the corrosion inhibitor using the method
according to the invention have been given as percentages by weight calculated in
reference to the total mass of the inhibitor.
The corrosion inhibitor produced on the basis of the mixture of modified imidazoline
derivatives is characterized by better anti-corrosion and hydrophilic properties as compared
to inhibitors containing known imidazoline derivatives.

The inhibitor according to this invention forms homogenous fluids with formation
water containing up to 30% salt, and even at a temperature of 80°C, no precipitation of the
inhibitor from these fluids is observed. The exceptional compatibility of the inhibitor that
is the subject of this invention with formation water of varying salinity increases its anti-
corrosion properties both in an aqueous phase and gaseous phase.
In the case where high transparency of the inhibitor that is the subject of this
invention is required during long-term storage under winter conditions at a temperature
below -30°C, it is beneficial to introduce a known imidazoline derivative into the
composition of the inhibitor, the small addition of which causes the inhibitor according to
this invention to be completely transparent.
In the case where high transparency of the inhibitor according to this invention is
required during long-term storage at a temperature below -40°C, aliphatic polyols,
preferably ethylene glycol, glycerin, propylene glycol, dipropylene glycol, tripropylene
glycol, or their mixtures can be applied in an amount from 0.5 to 50% by weight, and
optionally aliphatic alcohols containing from 1 to 6 carbon atoms per molecule other than
methanol, isopropanol, and ethanol.
The corrosion inhibitor produced according to the method of this invention forms a
stable protective film on metal surfaces and also protects against corrosion in the gaseous
phase, while not allowing corrosion to occur even in the most aggressive environments
containing carbon dioxide, hydrogen sulfide, and chlorides. The corrosion inhibitor
according to this invention is resistant to the high temperatures present in the deposit, and
does not exhibit tendencies of precipitation from formation water and precipitation of
sediments. The corrosion inhibitor is effective at low doses, at continuously dosing, from
10 to 80 ppm of natural gas and formation water. Its high anti-corrosion effectiveness
enables protection of extraction equipment not only against uniform corrosion, but also,
above all, against pitting corrosion. It protects metal surfaces against corrosion well, also in
the case of a periodical failure of the dosing system. An additional advantage of the
inhibitor according to this invention is that it exhibits no tendency of foaming in the
formation water-inhibitor system.
One of the numerous versions of the corrosion inhibitor according to this invention
contains benzoic acid, which may act as a bactericide.

In practice, water-soluble corrosion inhibitor for protection of lifting casings and natural
gas pipelines, according to the invention, is added to the gas - water continuously.
Corrosion inhibitor according to the invention, in general, is added to the fluid from about
0,01 to 5000 ppm, preferably from about 1 to 500 ppm, the most preferably from about 10
to 100 ppm.

The examples given below illustrate the invention while not limiting its scope.
Exemples from 1 to 5 concern the production of new mixture of modified imidazoline
derivatives, and examples from 6 to 11 concern the production of the corrosion inhibitor
according to the invention.

Example 1.

The following components were introduced into a reactor: 103.16 kg ( 1 mole)


diethylenetriamine, 141.23 kg (0.5 mole) distilled olein, in which the main component is
oleic acid C 18H3 2, and 45.02 kg (0.5 mole) oxalic acid. The content was heated while
being mixed constantly with a mechanical stirrer, and nitrogen barbotage was additionally
applied in order to remove the water forming during the reaction. After a temperature of
150°C was achieved, it was maintained for 3 hours until an acid number of 3.51 mg KOH/g
was obtained, and after that, further heating was applied until the temperature of 220°C
was achieved. The reaction was performed for 4 hours while the temperature was
maintained constant at 220°C and while nitrogen barbotage was applied for the purpose of
removing water from the reaction. 226 kg of product with acid number 0.25 mg KOH/g
were obtained.

Example 2 .
The following components were introduced into a reactor: 103.16 kg ( 1 mole)
diethylenetriamine, 279.64 kg (0.99 mole) oleic acid, and 1.88 kg (0.01 mole) azelaic acid.
The content was heated while being mixed constantly with a mechanical stirrer, and
nitrogen barbotage was additionally applied in order to remove the water forming during
the reaction. After a temperature of 150°C was achieved, it was maintained for 3 hours
(acid number 4.32 mg KOH/g was obtained), and after that, further heating was applied
until the temperature of 220°C was achieved. The reaction was performed for 5 hours while
the temperature was maintained constant at 220°C and while nitrogen barbotage was
applied for the purpose of removing water from the reaction. 3 17 kg of product (mixture of
modified imidazoline derivatives) with acid number = 0.38 mg KOH/g were obtained.

Example 3.
The following components were introduced into a reactor: 103.16 kg ( 1 mole)
diethylenetriamine, 264.10 kg (0.95 mole) tall oil fatty acids, and 10.1 1 kg (0.05 mole)
sebacic acid. The content was heated while being mixed constantly with a mechanical
stirrer, and nitrogen barbotage was additionally applied in order to remove the water
forming during the reaction. After a temperature of 150°C was achieved, it was maintained
for 3 hours (acid number 5.1 mg KOH/g was obtained), and after that, further heating was
applied until the temperature of 220°C was achieved. The reaction was performed for 5
hours while the temperature was maintained constant at 220°C and while nitrogen
barbotage was applied for the purpose of removing water from the reaction. 308 kg of
product (mixture of modified imidazoline derivatives) with acid number 0.7 mg KOH g
were obtained.
Example 4 .
The following components were introduced into a reactor: 103.16 kg ( 1 mole)
diethylenetriamine, 268.34 kg (0.95 mole) distilled olein, in which the main component is
oleic acid C 18 H34 0 2, and 5.90 kg (0.05 mole) succinic acid. The content was heated while
being mixed constantly with a mechanical stirrer, and nitrogen barbotage was additionally
applied in order to remove the water forming during the reaction. After a temperature of
150°C was achieved, it was maintained for 3 hours (acid number 3.94 mg KOH/g was
obtained), and after that, further heating was applied until the temperature of 210°C was
achieved. The reaction was performed for 5 hours while the temperature was maintained
constant at 210°C and while nitrogen barbotage was applied for the purpose of removing
water from the reaction. 312 kg of product (mixture of modified imidazoline derivatives)
with acid number 0.24 mg KOH/g were obtained.

Example 5.
The following components were introduced into a reactor: 103.16 kg ( 1 mole)
diethylenetriamine, 268.34 kg (0.95 mole) distilled olein, in which the main component is
oleic acid 18
Η34 0 2 and 7.67 kg (0.05 mole) adipic acid. The content was heated while
being mixed continuously with a mechanical stirrer and at the same time, a 100 mm Hg
vacuum was applied in order to remove water from the reaction. After a temperature of
150°C was achieved, it was maintained for 3 hours (acid number = 4.72 mg KOH/g was
obtained), and after that, further heating was applied until the temperature of 220°C was
achieved. The reaction was performed for 5 hours while the temperature was maintained
constant at 220°C and while a 100 mmHg vacuum was applied for the purpose of removing
water from the reaction. 299 kg of product (mixture of modified imidazoline derivatives)
with acid number 0.33 mg KOH/g were obtained.

Example 6.
The following components were introduced into a reactor: 440.9 kg (44.09 % by
weight) of methyl alcohol, 400 kg (40 % by weight) of isopropyl alcohol, and then 66 kg
(6.6 % by weight) of the product of condensation of diethylenetriamine with distilled olein
and sebacic acid, produced according to example 3, with acid number 0.7 mg KOH/g,
with the difference that in the condensation process instead of tall oil fatty acids distilled
olein was used in the amount of 0.95 mole for 1 mole of diethylenetriamine and 0.05 mole
of sebacic acid. After complete dissolution, 33 kg (3.3 % by weight) of glacial acetic acid
were added. After the reaction was fully completed at room temperature to neutral pH, 10
kg (1% by weight) of oxyethylenated hydrogenated tall oil amine, containing 5 ethoxyl
groups per molecule and 20 kg (2 % by weight) of glycerin were added. After complete
dissolution, 30 kg (3 % by weight) of 3-methoxypropyloamine and 0.1 kg (0.01 % by
weight) of a siloxane derivative with the commercial name Foam Ban HP 732 from the
Miinzing company were added. After complete dissolution at room temperature, 1000 kg
(100 % by weight) of corrosion inhibitor were obtained, which is a clear, low-viscosity
liquid with a poor point below - 60 °C and a kinematic viscosity of 2.7 mm /s at a
temperature of 20°C.

Example 7.
The following components were introduced into a reactor: 405.0 kg (40.5 % by
weight) of methyl alcohol, 302 kg (30.2 % by weight) of isopropyl alcohol, and then 150
kg (15.0 % by weight) of the product of condensation of diethylenetriamine with the fatty
acids of tall oil and azelaic acid, produced according to example 2, with acid number 0.4
mg KOH/g, with the difference that in the condensation process instead of oleic acid tall
oil fatty acids were used in the amount of 0.99 mole for 1 mole of diethylenetriamine and
0.01 mole of azelaic acid. After complete dissolution, 90 kg (9 % by weight) of benzoic
acid were added. After the reaction was fully completed at room temperature to neutral pH,
7 kg (0.7 % by weight) of ethoxylated hydrogenated tall oil amine, containing 6 ethoxyl
groups per molecule and 5 kg (0.5 % by weight) of ethylene glycol were added. After
complete dissolution, 40 kg (4% by weight) of 3-methoxypropyloamine and then 1 kg (0.1
% by weight) of a siloxane derivative with the commercial name Foam Ban HP 732 from
the Miinzing company were added. After complete dissolution at room temperature, 1000
kg (100 % by weight) of corrosion inhibitor were obtained, which is a clear, low-viscosity
liquid with a poor point of - 60 °C and a kinematic viscosity of 7.6 mm2/s at a temperature
of20°C.

Example 8.
The following components were introduced into a reactor: 79 kg (7.9 % by weight)
of water, 150 kg (15 % by weight) of isopropanol, 100 kg (10 % by weight) of ethanol, and
200 kg (20 % by weight) of the product of condensation of diethylenetriamine, tall oil
acids, and adipic acid, produced according to example 5, with acid number 0.3 mg KOH/g,
with the difference that in the condensation process instead of distilled olein tall oil fatty
acids were used in the amount of 0.95 mole for 1 mole of diethylenetriamine and 0.05 mole
of adipic acid. After complete dissolution, 1 10 kg ( 1 % by weight) of glacial acetic acid
were added. After the reaction was fully completed at room temperature to neutral pH, 100
kg (10 % by weight) of oxyethylenated hydrogenated tall oil amine, containing 5 ethoxyl
groups per molecule were added. After complete dissolution, 50 kg (5 % by weight) of 3-
methoxypropyloamine, 100 kg (10 % by weight) of monoethanolamine, 100 kg (10% by
weight) of diethylamine, 10 kg ( 1 % by weight) of dipropylene glycol monomethyl ether,
and then 1 kg (0. 1 % by weight) of a siloxane derivative with the commercial name Foam
Ban HP 732 from the Miinzing company, were added. After complete dissolution at room
temperature, 1000 kg (100 % by weight) of corrosion inhibitor were obtained, which is a
clear liquid with a poor point of - 30 °C and a kinematic viscosity of 37 mm /s at a
temperature of 20°C.

Example 9.
The following components were introduced into a reactor: 770 kg (77% by weight)
methyl alcohol, 80 kg (8 % by weight) of the product of condensation of
diethylenetriamine, distilled olein, in which the main component is oleic acid C 340 2 and
succinic acid, produced according to example 4, with acid number 0.25 mg KOH/g, and 20
kg (2 % by weight) of the known product of condensation of diethylenetriamine and oleic
acid. After complete dissolution, 40 kg (4 % by weight) of glacial acetic acid were added.
After the reaction was fully completed at room temperature to neutral pH, 10 kg ( 1 % by
weight) of oxyethylenated, hydrogenated tall oil amine, containing 5 ethoxyl groups per
molecule, were added, and after the temperature was lowered to room temperature, 40 kg
(4 % by weight) of 3-methoxypropyloamine and 30 kg (3 % by weight) of diethylamine,
and then 10 kg ( 1 % by weight) of a siloxane derivative with the commercial name Foam
Ban HP 732, from the Miinzing company, were added. After complete dissolution at room
temperature, 1000 kg (100 % by weight) of corrosion inhibitor were obtained, which is a
clear, low-viscosity liquid with a poor point below - 60 °C, a kinematic viscosity of 4.5
mm2/s at a temperature of 20°C, and high transparency during storage at a temperature of
-40°C for a period of 1 year.

Example 10.
The following components were introduced into a reactor: 177.9 kg (17.79 % by
weight) of isopropyl alcohol, and then 500 kg (50 % by weight) of the product of
condensation of diethylenetriamine with oleic acid (oleic acid C 1 H340 2 is the main
component in distilled olein) and oxalic acid, produced according to example 1, with acid
number 0.25 mg KOH/g. After complete dissolution, 250 kg (25 % by weight) of glacial
acetic acid were added. After the reaction was fully completed at room temperature to
neutral pH, 0.1 kg (0.01 % by weight) of oxyethylenated hydrogenated tall oil amine,
containing 5 ethoxyl groups per molecule, and 50 kg (5 % by weight) of diethylene glycol
butyl ether were added. Next, 1 kg (0.1 % by weight) monoethanolamine and 1 kg (0.1 %
by weight) diethylamine, and then 20 kg (2 % by weight) of a siloxane derivative with the
commercial name Foam Ban HP 732, from the Miinzing company, were added. After
complete dissolution at room temperature, 1000 kg (100 % by weight) of corrosion
inhibitor were obtained, which is a clear liquid with a poor point of - 45 °C and a kinematic
viscosity of 57 mm 2/s at a temperature of 20°C.

Example 1 1.
The following components were introduced into a reactor: 596.72 kg (59.672 % by
weight) of methyl alcohol, 400 kg (40 % by weight) of isopropyl alcohol, and then 1.32 kg
(0.132 % by weight) of the product of condensation of diethylenetriamine with distilled
olein (oleic acid C18 H3402 is the main component in distilled olein) and sebacic acid,
produced according to example 3, with acid number 0.7 mg KOH/g, with the difference
that in the condensation process instead of tall oil fatty acids distilled olein was used in the
amount of 0.95 mole for 1 mole of diethylenetriamine and 0.05 mole of sebacic acid. After
complete dissolution, 0.66 kg (0.066 % by weight) of glacial acetic acid were added. After
the reaction was fully completed at room temperature to neutral pH, 0.2 kg (0.02 % by
weight) of oxyethylenated hydrogenated tall oil amine, containing 5 ethoxyl groups per
molecule, and 0.4 kg (0.04 % by weight) of propylene glycol were added. After complete
dissolution, 0.6 kg (0.06 % by weight) of 3-methoxypropyloamine and 0.1 kg (0.01 % by
weight) of a siloxane derivative with the commercial name Foam Ban HP 732 from the
Miinzing company were added. After complete dissolution at room temperature, 1000 kg
(100 % by weight) of corrosion inhibitor were obtained, which is a clear, low-viscosity
liquid with a poor point below - 60 °C and a kinematic viscosity of 1.2 mm /s at a
temperature of 20°C.

In gas wells equipped with high-output dosing pumps, a corrosion inhibitor with low
kinematic and dynamic viscosity over a wide temperature range is required, and thus, a low
content of active components is also required. Required inhibitor dosages may be 1000,
2000, or 3000 ppm for water-gas system while continuous dosing. The corrosion inhibitor
according to example 11 is destined for such dosing pumps.
Example 12 - comparative.
The following components were introduced into a reactor: 440.9 kg (44.09 % by
weight) of methyl alcohol, 400 kg (40 % by weight) of isopropyl alcohol, and then 66 kg
(6.6 % by weight) of the known product of condensation of diethylenetriamine with
distilled olein according to formula ( Γ), with acid number 1.1 mg KOH/g. After complete
dissolution, 33 kg (3.3 % by weight) of glacial acetic acid were added. After the reaction
was fully completed at room temperature to neutral pH, a product with formula (5') was
obtained.
Next, 10 kg ( 1 % by weight) of oxyethylenated, hydrogenated tall oil amine, containing 5
ethoxyl groups per molecule, and 20 kg (2 % by weight) of glycerin were added. After
complete dissolution, 30 kg (3 % by weight) of 3-methoxypropyloamine and 0.1 kg (0.01
% by weight) of a siloxane derivative with the commercial name Foam Ban HP 732 from
the Miinzing company were added. After complete dissolution at room temperature, 1000
kg (100 % by weight) of corrosion inhibitor were obtained, which is a clear, low-viscosity
liquid with a poor point below - 60 °C and a kinematic viscosity of 2.9 mm /s at a
temperature of 20°C.

Example 13.
Tests of the anti-corrosion properties of the water-soluble corrosion inhibitor for
protection of natural gas bore-holes and pipelines according to this invention were
performed according to the Wheel Test in accordance with standard ASTM NACE 1 D 182
"Wheel test method used for evaluation of film-persistent corrosion inhibitors for Oilfield
applications". This is a conventional method of testing mass decrement, used to evaluate
the effectiveness of an inhibitor through simulation of continuous flow of a corrosive
medium.
A. Preparation of corrosive water: corrosive water was prepared according to the following
composition: 9.62 % by weight NaCl and 0.305 % by weight CaCl2 and 0.186 % by weight
MgCl2 -6H20 and 89.89 % by weight distilled water. The water was subjected to nitrogen
barbotage for 30 minutes, and then to carbon dioxide barbotage for approx. 10 minutes
until the achievement of corrosive water pH within the range of 4.4 to 4.8.

B. Preparation of paraffin oil (mixture of isoparaffmic hydrocarbons): oil was


homogenized at a temperature of 62°C, and then poured into test bottles.
C. Preparation of metal samples: metal plates of „Sand blasted mild steel Shim stock" type,
with dimensions of 0.13x12.7x76 mm were rinsed with acetone, dried with a dry cloth,
weighed, and stored in a desiccator.

90 ml corrosive water and 10 ml paraffin oil were added into bottled with a capacity of 200
ml from which air had been removed earlier. Next, the inhibitor according to the invention
from example 6, 7, 8, 9, 10 was added in the amount of 30, 50, and 80 ppm by weight, and
the inhibitor according to the invention from example 11 in the amount of 1500, 2500 ppm
by weight, to the corrosive medium. The metal plates described in point C) were
introduced into the thus prepared bottles. Carbon dioxide was once again dosed into the
bottles over a time of approx. 30 s, and bottles were hermetically closed. The bottles were
placed in a thermostat at a temperature of 65.5°C, in a rotating apparatus that rotated with a
speed of 15 rotations/minute. The test was performed for a period of 72 hours. After the
test, metal samples were removed from bottles, rinsed with isopropyl alcohol, and
subjected to the action of a 10 % hydrochloric acid solution for a period of 10 - 15 seconds.
Metal samples were then rinsed with water, acetone, and alcohol, after which they were
weighed with an accuracy to 0.1 mg. The mass decrement of metal samples was assessed,
and the possible presence of pitting corrosion was also assessed.

The percentage of protection against corrosion was calculated from the mass decrement of
the metal sample in the presence of the inhibitor W(inhib) and without the inhibitor W(0).

Percentage of protection, % P = W (0) - W(inhib) / W(0) x 100%

The results of tests of the anti-corrosion properties of corrosion inhibitors according to


examples 6, 7, 8, 10, and 11 containing a neutralized, new mixture of modified imidazoline
derivatives according to the invention, according to formula (5) and (6), as well as the
results of tests of anti-corrosion properties of the corrosion inhibitor according to example
9, containing a neutralized mixture of modified imidazoline derivatives according to the
invention, according to formula (5), (6), and (5'), in comparison to the corrosion inhibitor
produced according to example 12 containing a neutralized known product produced by a
known method in the reaction of condensation of diethylenetriamine with oleic acid
according to formula (5') in place of the neutralized mixture of modified imidazoline
derivatives according to formula (5) and (6), are presented in the table below.
Water-soluble corrosion inhibitor according to the invention, Neutralized known
containing a neutralized mixture of modified imidazoline product produced by a
derivatives, according to formulae (5), (6) in examples 6, 7, 8, 10, known method in the
11 and a neutralized mixture of modified imidazoline derivatives reaction of
according to the invention according to formulae (5), (6), and (5') condensation of
in example 9 diethylenetriamine
with oleic acid
according to formula
(5')

According to 6 7 8 9 10 11 12
example

Concentration of [% protection [% protection]


corrosion inhibitor
in corrosive
medium
[ppm by weight]

30 72 91 96 82 97 - 53

50 80 92 98 86 98 - 69

80 94 96 98 95 98 - 85

1500 - - - - - 71

2500 - - - - - 81

INDUSTRIAL APPLICABILITY

The above examples proved that the water-soluble corrosion inhibitor for protection of
lifting casings and natural gas pipelines as well as the method of its production, according
to this invention are expected to find industrial applicability.
CLAIMS

1. The water-soluble corrosion inhibitor for protection of natural gas lifting casings
and pipelines containing imidazoline derivatives, oxyethylenated fatty amines, low-boiling
amines and alcohol solvents, characterized in that it contains:
- component a) in an amount from 0.15 to 75 % by weight, preferably from 1.5 to 35 % by
weight, obtained by neutralization from 0.1 to 50 % by weight, preferably from 1 to 30 %
by weight, of the new mixture of modified imidazoline derivatives, which is a product of
condensation of diethylenetriamine with fatty acids containing from 12 to 22 carbon atoms
per molecule and aliphatic dicarboxylic acids containing from 2 to 12 carbon atoms per
molecule, which constitutes a mixture of substances of general formulae (1) and (2),

wherein Ri: C 12 -C2 2 (1)

wherein R2 : C -C 12 (2),

with the optional addition of from 0.05 to 20 % by weight of the known product of
condensation of diethylenetriamine with fatty acids containing from 12 to 24 carbon atoms
per molecule, produced by a known method at a temperature of 180-280°C, preferably
220-260°C, of general formula ( )

wherein R3 : C 2-C24 ( )

with an aliphatic and/or aromatic monocarboxylic acid containing from 1 to 7 carbon


atoms per molecule, used in an amount from 0.05 to 25 % by weight, where the mass ratio
of the mixture of compounds of general formulae (1), (2), and optionally ( ) to
monocarboxylic acid is 1 : 0.15 - 0.70, with obtaining of the final product, which is a
mixture of compounds of general formulae (5), (6), and optionally (5')

wherein R C 12 -C22 (5)


R : H, - s, aromatic radical (C H )

wherein R2 : C2- 2 (6)


R H, C -C , aromatic radical (C H )

wherein R3 : C12 -C24 (5 ' )


¾ : H, CrC , aromatic radical (C6H )

- component b) that is oxyethylenated fatty amines containing from 14 to 22 carbon atoms


per molecule and from 2 to 20, preferably from 3 to 15, ethoxyl groups per molecule, in an
amount from 0.01 to 10 % by weight;
- component c) that is alkalizing agent in an amount from 0.06 to 25 % by weight,
preferably from 1 to 20 % by weight;
- optional component d) that is aliphatic polyols in an amount from 0.04 to 50 % by
weight; *
- component e) that is aliphatic alcohols containing from 1 to 6 carbon atoms per molecule,
optionally with the addition of water, in an amount from 15 to 99.7 % by weight
and
- component f that is anti-foaming agent in an amount from 0.01 to 2 % by weight.

2. The corrosion inhibitor according to claim 1, characterized in that it contains as


component a) a product formed by neutralization with acetic acid and/or benzoic acid of
the following imidazoline derivatives:
i) the new mixture of modified imidazoline derivatives, which is condensation product of
diethylenetriamine with fatty acids containing 12-22 carbon atoms per molecule and
aliphatic dicarboxylic acids containing 6-10 carbon atoms per molecule, where the molar
ratio of diethylenetriamine to fatty acids and to aliphatic dicarboxylic acids is 1: 0,5-0,99:
0.01-0.5, at a temperature of at least 140°C, preferably 150°C, with the formation of an
aminoamide mixture of general formulae (3) and (4),
wherein Ri: C 12 -C22 ( 3)

wherein R2 : C -C 10 ( 4)

with acid number < 10 mg KOH/g,

and next, the temperature is raised to above 180°C, preferably to 220°C, and the
condensation reaction is performed further until a mixture of compounds of general
formulae (1) and (2) is obtained
with acid number < 1 mg KOH/g,

ii) optionally added, the known product of condensation of diethylenetriamine with fatty
acids.

3. The corrosion inhibitor according to claim 1 or 2, characterized in that as


component e) it contains methanol, isopropanol, ethanol, or their mixtures.
4. The corrosion inhibitor according to claim 1 or 2, characterized in that as
component d) it contains ethylene glycol, glycerin, propylene glycol, dipropylene glycol,
tripropylene glycol, or their mixtures.
5. The corrosion inhibitor according to claim 1 or 2, characterized in that as
component c) it contains 3-methoxypropylamine, 2-aminoethanol (monoethanolamine),
diethyloamine, or their mixtures.
6. The corrosion inhibitor according to claims 1 or 2, characterized in that as
component f) it contains a siloxane derivative, preferably with branched siloxane
polymers.
7. The method of production of the water-soluble corrosion inhibitor for protection of
natural gas lifting casings and pipelines encompassing neutralization of the imidazoline
derivative and addition of further inhibitor components, characterized in that it consists
of the following stages:
I) production of component a), that is neutralization carried out at room temperature
in a reaction medium containing component e), that is aliphatic alcohols containing from 1
to 6 carbon atoms per molecule, optionally with the addition of water, in an amount from
15 to 99.7 % by weight, of the new mixture of modified imidazoline derivatives that is the

product of condensation of diethylenetriamine with fatty acids containing from 12 to 22


carbon atoms per molecule and aliphatic dicarboxylic acids containing from 2 to 12 carbon
atoms per molecule, constituting a mixture of compounds of general formulae (1) and (2),

wherein R \ C i2-C 2 (1)


wherein R2 : C2-C 12 (2)

used in an amount from 0.1 to 50 % by weight, preferably from 1 to 30 % by weight, with


the optional addition of 0.05 to 20 % by weight of the known product of condensation of
diethylenetriamine with fatty acids containing from 12 to 24 carbon atoms per molecule,
produced by a known method at a temperature of 180-280°C, preferably 220-260°C, of
general formula ( ),

wherein R3 : C 12 -C24

with an aliphatic and/or aromatic monocarboxylic acid containing from 1 to 7 carbon


atoms per molecule, used in an amount from 0.05 to 25 % by weight, where the mass ratio
of the mixture of compounds of general formulae (1), (2), and optionally ( Γ) to
monocarboxylic acid is 1 : 0.15 - 0.70, with obtaining of the final product, which is a
mixture of compounds of general formulae (5), (6), and optionally (5'),

wherein R : C 12 -C 22 ( 5)
R H, - , aromatic radical (C6H )

wherein R3 : C 2 -C24 ( 5' )

R 4 H, Ci-C , aromatic radical (C6H6)

II. introduction to component a), in an amount from 0.15 to 75 % by weight,


preferably from 1.5 to 35 % by weight, and to the mentioned component e), of further
inhibitor components:
component b), that is oxyethylenated fatty amines containing from 14 to 22 carbon atoms
and from 2 to 20, preferably from 3 to 15, ethoxyl groups per molecule, in an amount from
0.01 to 10 % by weight;
component c), which is an alkalizing agent in an amount from 0.06 to 25 % by weight,
preferably from 1 to 20 % by weight;
optionally component d), that is aliphatic polyols in an amount from 0.04 to 50 % by
weight,
and finally, component f), which is an anti-foaming agent in an amount from 0.01 to 2 %
by weight.

8. The method according to claim 7, characterized in that in I stage, neutralization with


glacial acetic acid is carried out of the following imidazoline derivatives:
i) the new mixture of modified imidazoline derivatives, which is condensation product of
diethylenetriamine with fatty acids containing 12-22 carbon atoms per molecule and
aliphatic dicarboxylic acids containing 6-10 carbon atoms per molecule, in which
condensation the molar ratio of diethylenetriamine to fatty acids and to aliphatic
dicarboxylic acids is 1:0,5-0,99: 0.01-0.5, at a temperature of at least 140°C, preferably
150°C, with the formation of an aminoamide mixture of general formulas (3) and (4),

with acid number < 10 mg KOH/g,

after which the temperature of the reaction is raised to above 180°C, preferably to 220°C,
and as a result of the reaction, a mixture of compounds of general formulae (1) and (2) is
obtained
with acid number < 1 mg KOH/g,
ii) optionally added the known product of condensation of diethylenetriamine with fatty
acids.
AMENDED CLAIMS
received by the International Bureau on 08 October 2014 (08.10.2014)

CLAIMS

1. The water-soluble corrosion inhibitor for protection of natural gas lifting casings
and pipelines containing imidazoline derivatives, oxyethylenated fatty amines, low-boiling
amines and alcohol solvents, characterized in that it contains:
- component a) in an amount from 0.15 to 75 % by weight, preferably from 1.5 to 35 % by
weight, obtained by neutralization from 0.1 to 50 % by weight, preferably from 1 to 30 %
by weight, of the new mixture of modified imidazoline derivatives, which is a product of
condensation of diethylenetriamine with fatty acids containing from 1 to 22 carbon atoms
per molecule and aliphatic dicarboxylic acids containing from 4 to 12 carbon atoms per
molecule, which constitutes a mixture of substances of general formulae (1) and (2),

wherein i C -C2 i (1)

wherein R 2 : C2-C10 (2),

with the optional addition of from 0.05 to 20 % by weight of the known product of
condensation of diethylenetriamine with fatty acids containing from 12 to 24 carbon atoms
per molecule, produced by a known method at a temperature of 180-280°C, preferably
220-260°C, of general formula (1')

wherein C -C (

with an aliphatic and or aromatic monocarboxylic acid containing from 1 to 7 carbon


atoms per molecule, used in an amount from 0.05 to 25 % by weight, where the mass ratio
of the mixture of compounds of general formulae (1), (2), and optionally ( Γ) to
monocarboxylic acid is 1: 0. - 0.70, with obtaining of the final product, which is a
mixture of compounds of general formulae (5), (6), and optionally (5')

herein R . C11-C21 (5)


R4: H, C -C , aromatic radical ( H5)

wherein R2 : C -C 1 (6)
R , Ci-Ce, aromatic radical (C H )

wherein R3: C -C2 3 (


R4: H, Ci-C , aromatic radical C H )

- component b) that is oxyethylenated fatty amines containing from to 22 carbon atoms


per molecule and from 2 to 20, preferably from 3 to 15, ethoxyl groups per molecule, in an
amount from 0.01 to 10 % by weight;
- component c) that is alkalizing agent in an amount from 0.06 to 25 % by weight,
preferably from 1 to 20 % by weight;
- optional component d) that is aliphatic poiyols in an amount from 0.04 to 50 % by
weight;
- component e) that is aliphatic alcohols containing from 1 to 6 carbon atoms per molecule,
optionally with the addition of water, in an amount from 15 to 99.7 % by weight
and
- component f that is anti-foaming agent in an amount from 0.01 to 2 % by weight.

2. The corrosion inhibitor according to claim 1, characterized in that it contains as


component a) a product formed by neutralization with acetic acid and/or benzoic acid of
the following imidazoline derivatives:
i) the new mixture of modified imidazoline derivatives, which is condensation product of
diethylenetriamine with fatty acids containing 12-22 carbon atoms per molecule and
aliphatic dicarboxylic acids containing 6-10 carbon atoms per molecule, where the molar
ratio of diethylenetriamine to fatty acids and to aliphatic dicarboxylic acids is : 0,80-0,99:
0,01-0,10, at a temperature of at least 140°C, preferably 150°C, with the formation of an
aminoamide mixture of general formulae (3) and (4),
wherein R : C11-C21 ( 3)

wherein R : C ( 4)

with acid number < 10 g H/g,

and next, the temperature is raised to above 180°C, preferably to 220°C, and the
condensation reaction is performed further until a mixture of compounds of general
formulae (1) and (2) is obtained

wherein C -C (1)

wherein R2 : C4-C8
with acid number < 1 g KOH/g,

ii) optionally added, the known product of condensation of diethylenetriamine with fatty
acids.

3. The corrosion inhibitor according to claim 1 or 2, characterized in that as


component e) it contains methanol, isopropanol, ethanol, or their mixtures.
4. The corrosion inhibitor according to claim 1 or 2, characterized in that as
component d) it contains ethylene glycol, glycerin, propylene glycol, dipropylene glycol,
tripropylene glycol, or their mixtures.
5. The corrosion inhibitor according to claim 1 or 2, characterized in that as
component c) it contains 3-methoxypropylamine, 2-aminoethanol (monoethanolamine),
diethyloamine, or their mixtures.
6. The corrosion inhibitor according to claims 1 or 2, characterized in that as
component ) it contains a siloxane derivative, preferably with branched siloxane
polymers.
7. The method of production of the water-soluble corrosion inhibitor for protection of
natural gas lifting casings and pipelines encompassing neutralization of the imidazoline
derivative and addition of further inhibitor components, characterized in that it consists
of the following stages:
I) production of component a), that is neutralization carried out at room temperature
in a reaction medium containing component e), that is aliphatic alcohols containing from 1
to 6 carbon atoms per molecule, optionally with the addition of water, in an amount from
15 to 99.7 % by weight, of the new mixture of modified imidazoline derivatives that is the
product of condensation of diethylenetriamine with fatty acids containing from to 22
carbon atoms per molecule and aliphatic dicarboxylic acids containing from 4 to 12 carbon
atoms per molecule, constituting a mixture of compounds of general formulae (1) and (2),

wherein Ri: C -C i (1)


wherein 2 C2-C10 (2)

used in an amount from 0.1 to 50 % by weight, preferably from 1 to 30 % by weight, with


the optional addition of 0.05 to 20 % by weight of the known product of condensation of
diethylenetriamine with fatty acids containing from 2 to 24 carbon atoms per molecule,
produced by a known method at a temperature of 180-280°C, preferably 220-260°C, of
general formula ( ),

wherein . Ci -C

with an aliphatic and/or aromatic monocarboxylic acid containing from 1 to 7 carbon


atoms per molecule, used in an amount from 0.05 to 25 % by weight, where the mass ratio
of the mixture of compounds of general formulae (1), (2), and optionally ( ) to
monocarboxylic acid is 1: 0.15 - 0.70, with obtaining of the final product, which is a
mixture of compounds of general formulae (5), (6), and optionally (5'),

wherein R : C11-C21 ( 5)
R4: H, C -C , aromatic radical $

wherein R : C2-C10 ( 6)

R4: H , Ci-Ce, aromatic radical ( ¾)

wherein R3: C 11-C23 -

:H Ci-C aromatic radical (C6H

II. introduction to component a), in an amount from 0.15 to 75 % by weight,


preferably from 1.5 to 35 % by weight, and to the mentioned component e), of further
inhibitor components:
component b), that is oxyethylenated fatty amines contaimng from 14 to 22 carbon atoms
and from 2 to 20, preferably from 3 to 15, ethoxyl groups per molecule, in an amount from
0.01 to 10 % by weight;
component c), which is an alkalizing agent in an amount from 0.06 to 25 % by weight,
preferably from 1 to 20 % by weight;
optionally component d), that is aliphatic polyols in an amount from 0.04 to 50 % by
weight,
and finally, component f , which is an anti-foaming agent in an amount from 0.01 to 2 %
by weight.

8. The method according to claim 7, characterized in that in I stage, neutralization with


glacial acetic acid is carried out of the following imidazoline derivatives:
i) the new mixture of modified imidazoline derivatives, which is condensation product of
diethylenetriamine with fatty acids containing 12-22 carbon atoms per molecule and
aliphatic dicarboxylic acids containing 6-10 carbon atoms per molecule, in which
condensation the molar ratio of diethylenetriamine to fatty acids and to aliphatic
dicarboxylic acids is 1:0,80-0,99: 0,01-0,10, at a temperature of at least 140°C, preferably
150°C, with the formation of an aminoamide mixture of general formulas (3) and (4),

with acid number < 10 g KOH/g,

after which the temperature of the reaction is raised to above 180°C, preferably to 220°C,
and as a result of the reaction, a mixture of compounds of general formulae (1) and (2) is
obtained
wherein R : C -C2i (1)

wherein R2 : C4-C

with acid number < 1 mg KOH/g,


ii) optionally added the known product of condensation of diethylenetriamine with fatty
acids.
STATEMENT under Article 19(1)

The applicant hereby states that Claims were amended under Article 19
as follows:

There was an amendment in the range of aliphatic dicarboxylic acids


condensed with diethylenetriamine - limitation t o those containing from 4 t o
12 carbon atoms; this amendment resulted in amending the number of carbon
atoms in alkylene group, which couples two imidazoline rings (substituent R ).
The amendment makes claims 1, 2, 7 and 8 clear and thus allows t o clarify the
scope of protection of the invention. On the other hand, the amendment
requires the same amendments t o be introduced in the description in due
time. Moreover, examples 1 and 10 need t o be removed from the description
since they relate t o oxalic acid (dicarboxylic acid having 2 carbon atoms), so
they are outside the scope of the claims.

Another amendment referred t o molar ratio of diethylenetriamine t o fatty


acids and t o aliphatic dicarboxylic acids (claims 2 and 8). The amendment

aimed t o reflect the required stoichiometry for the reaction of the amine and
the fatty acids and the aliphatic dicarboxylic acids, as well as t o make the claims
2 and 8 clear. The amendment requires the same amendments t o be
introduced in the description in due time.

t was also necessary t o amend the number of carbon atoms in substituents R


and R3 . The aim of the amendment was t o make definition of the alkyl rests
consistent with the disclosed carboxylic acids. The amendment requires the
same amendments t o be introduced in the description in due time.

The number of hydrogen atoms in aromatic radical (substituent R ) was


amended, making the claims 1 and 7 clear. The amendment requires the same
amendments t o be introduced in the description in due time.
A . CLASSIFICATION O F SUBJECT MATTER
INV. C09K8/54 C23F11/14
ADD.

According to International Patent Classification (IPC) o r t o both national classification and IPC

B . FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)
C09K E21B C23F

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPO-Internal , WPI Data

C . DOCUMENTS CONSIDERED TO B E RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

Y AU 458 663 B2 (TEXACO DEVELOPMENT CORP. ) 1-8


17 February 1975 (1975-02-17)
c l aims 1 , 9 ; exampl e 1 ; tabl e 1

Y US 2 646 399 A (HUGHES WI LLIAM B) 1-8


2 1 July 1953 (1953-07-21)
col umn 3 , l i nes 57-71 ; c l aims 5 , 8

Y US 6 395 225 Bl (POU TONG EAK [FR] ET AL) 1-8


28 May 2002 (2002-05-28)
col umn 2 , l i ne 36 - col umn 3 , l i ne 7 ;
c l aims 1 ,4,5

A US 3 629 104 A (MADD0X JIM JR) 1-8


2 1 December 1971 (1971-12-21)
c i ted i n the appl i cati on
col umn 4 , l i nes 8-11 ; c l aims 1 , 2 ; exampl e
1

-/--
X| Further documents are listed in the continuation of Box C . XI See patent family annex.

* Special categories of cited documents :


"T" later document published after the international filing date o r priority
date and not in conflict with the application but cited to understand
"A" document defining the general state of the art which is not considered
the principle o r theory underlying the invention
to be of particular relevance
"E" earlier application o r patent but published o n o r after the international
"X" document of particular relevance; the claimed invention cannot be
filing date considered novel o r cannot b e considered to involve a n inventive
"L" documentwhich may throw doubts o n priority claim(s) orwhich is step when the document is taken alone
cited to establish the publication date of another citation o r other
"Y" document of particular relevance; the claimed invention cannot be
special reason (as specified)
considered to involve a n inventive step when the document is
"O" document referring to a n oral disclosure, use, exhibition o r other combined with one o r more other such documents, such combination
means being obvious to a person skilled in the art
"P" document published prior to the international filing date but later than
the priority date claimed "&" document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report

8 August 2014 21/08/2014


Name and mailing address of the ISA/ Authorized officer
European Patent Office, P.B. 5818 Patentlaan 2
N L - 2280 HV Rijswijk
Tel. (+31-70) 340-2040,
Fax: (+31-70) 340-3016 Redecker, Mi chael
C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

US 2005/156137 Al (OVERKEMPE KORNELIS [NL] 1-8


ET AL) 2 1 July 2005 (2005-07-21)
c i ted i n the appl i cati on
paragraphs [0001] , [0045] ; c l aim 1 ;
tabl e s 2 , 4

US 2 878 234 A (PETERSON LOWELL E) 1-8


17 March 1959 (1959-03-17)
c l aim 1 ; exampl e VI

US 2 889 193 A (DENMAN WAYNE L ET AL) 1-8


2 June 1959 (1959-06-02)
col umn 4 , l i nes 62-71 ; c l aim 1
col umn 5 , l i nes 12-19

US 3 390 085 A ( FL0ECK PETER E) 1-8


25 June 1968 (1968-06-25)
col umn 3 , l i ne 53 - col umn 4 , l i ne 2 ;
c l aims 1 , 5 ; exampl e 1
Patent document Publication Patent family Publication
cited in search report date member(s) date

A U 458663 B2 17 -02- 1975 AU 458663 B2 17-02-1975


AU 3105071 A 11-01-1973

US 2646399 A 2 1-07- 1953 NONE

US 6395225 Bl 28 -05- 2002 AT 201240 T 15-06-2001


AU 730939 B2 22-03-2001
AU 6505398 A 12-10-1998
DE 69800800 Dl 21-06-2001
DE 69800800 T2 04-10-2001
EP 0968323 Al 05-01-2000
NO 994525 A 17-09-1999
OA 11160 A 16-04-2003
US 6395225 Bl 28-05-2002
O 9841673 Al 24-09-1998

US 3629104 A 2 1-12- 1971 NONE

US 2005156137 Al 2 1-07- 2005 AU 2002358067 Al 09-07-2003


GB 2399082 A 08-09-2004
SE 0104176 A 13-06-2003
US 2005156137 Al 21-07-2005
US 2013233543 Al 12-09-2013
O 03054251 A2 03-07-2003

US 2878234 A 17 -03- 1959 NONE

us 2889193 A 02 -06- 1959 NONE

us 3390085 A 25 -06- 1968 NONE