Beruflich Dokumente
Kultur Dokumente
(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:
BACKGROUND ART:
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.
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.
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.
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.
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 ( )
wherein (5)
R4: H, C!-C , aromatic radical (C H6)
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 R 3: C 12 -C 24 (
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:
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),
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
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
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.
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
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.
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.
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).
According to 6 7 8 9 10 11 12
example
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 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 ( )
wherein R2 : C -C 10 ( 4)
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.
wherein R3 : C 12 -C24
wherein R : C 12 -C 22 ( 5)
R H, - , aromatic radical (C6H )
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),
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 (
wherein R2 : C -C 1 (6)
R , Ci-Ce, aromatic radical (C H )
wherein R : C ( 4)
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.
wherein . Ci -C
wherein R : C11-C21 ( 5)
R4: H, C -C , aromatic radical $
wherein R : C2-C10 ( 6)
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
The applicant hereby states that Claims were amended under Article 19
as follows:
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.
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)
Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.
-/--
X| Further documents are listed in the continuation of Box C . XI See patent family annex.
Date of the actual completion of the international search Date of mailing of the international search report
Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.