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CORROSION INHIBITOR BASED ON CHLORINE-CONTAINING
WASTE
1
Bilalova D.D.,
1
Turobjonov S.M.,
2
Kadirov Kh.I.
1
Tashkent State Technical University, Tashkent
2
Tashkent Chemical-Technological Institute, Tashkent
https://doi.org/10.5281/zenodo.15525994
Abstract
. The aim of the research is to determine the inhibitory properties
of the product of the interaction of chlorine-containing waste with
diethanolamine. The object of the research is the water of oil production and
processing enterprises, in particular, the North Urtabulak field under the
jurisdiction of Mubarekneftegaz.
Keywords:
corrosion inhibitor, oil, surfactants, chlorine waste, anti-
corrosion coatings
In the last decade, the use of organic and inorganic compounds as corrosion
inhibitors has become irrelevant over time, as their toxicity to the environment
has raised concerns about their use. Controlling the rate of metal corrosion by
nanomaterials is a way to highlight a new discovery in nanotechnology.
Nanomaterials have higher anti-corrosion properties, and their additives are
good corrosion inhibitors due to their larger surface-to-volume ratio compared
to conventional macroscopic materials. Many processes have been used to
prepare nanoparticles, and various researchers have successfully demonstrated
the applicability of nanomaterials as corrosion inhibitors [1,2].
BASF Company offers a coating inhibitor [3] for use in oil fields based on
polymers or oligomers of poly acid polyester, alkoxylated alcohol, or polyamine
condensate of fatty acid, which also contain surfactants; a corrosion inhibitor is
used for acidic systems, including ammonium iodide ion, a primary carbonyl
compound containing alkyl or an aromatic group containing from 1 to 6 carbon
atoms, alkyl or aromatic groups in turn may additionally contain nitrogen,
phosphorus, halogen, or a second oxygen fragment [4]; a corrosion inhibitor and
a composition based on it, including contact of a metal surface with an acidic
liquid containing a water base liquid, acid, as well as a strengthening composition
containing a compound that corresponds to the formula R
1
R
2
XCCOOH, where X
is a halogen, R
1
is C
1
-C
20
alkyl groups, C
3
-C
20
cycloalkyl groups, R
2
contains at least
one oxialkyl C
1
-C
20
and an aryl group C
6
-C
20
[5]; based on acrylonitrile, the
inhibitor Ifhangaz-1 was synthesized, developed by the Institute of Physical and
Inorganic Chemistry of the Russian Academy of Sciences jointly with the VNI Gaz
and the Volgograd branch of the VNI PAV Minneftechemprom [6]; anti-corrosion
coatings have found wide application in protecting metals from corrosion,
among which PINS [7] occupies an important place, which represents a complex
mixture of corrosion inhibitors, plasticizers, and protective components in
organic solvents; in the works [8] universal corrosion inhibitors based on amino
phenols, as well as "SNPX" heterocyclic amines (alkyl-[poly- (ethylene oxy) ]-
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phosphoryl pyridines, alkyl-[poly- (ethylene oxy) ]-phosph.
The purpose of this work is to determine the inhibitory properties of the
product of the interaction of the chlorine-containing waste with diethanolamine.
The water of oil production and processing enterprises, namely the North
Urtabulok field under the "Muborakneftegaz" Production Association, was
selected as the research object.
When extracting crude oil, to free it from mineral salts, it is washed with
water. Water after settling and separation is used in the reservoir pressure
maintenance system. For oil flushing, reservoir or furrow water heavily
contaminated with mineral salts is typically used (Table 1).
Table 1
Analysis* of the water of Northern Urtabulak under the "Muborakneftegaz" UE
Cations
Content in liters
Other definitions
mg/l
mg-eq/l
%-eq/l
Na
+
21332
927,50
65
Hardness mg-eq/l
General
505,00
K
+
30
0,77
-
Removable
NH
4+
150
2,42
-
Carbonate
4,30
Ca
2+
8000
400,00
28
Non-carbonate
500,70
Mg
2+
1276
105,00
7
рН
7,20
Fe
3+
<0,3
CO
2
free. mg/l
n/о
Fe
2+
<0,3
CO
2
agr. mg/l
n/о
Total
1435,69
100
Oxidation capacity mg O
2
/l
Anions
Content in liters
SiO
2
mg/l
n/о
mg/l
mg-eq/l
%-eq/l
Н
2
S
mg/l
7,16
Cl
–
49644
1400,00
98
РО
4
mg/l
SO
42-
1230
25,63
2
The
dry
residue
is
experimental.
84614
NO
2-
<0,01
Calculated.
82150
NO
3-
357
5,76
-
Physical properties:
Cont.
CO
3-
нет
Transparency
HCO
3-
262
4,30
-
Taste
brine
Total
1435,69
100
Color
Analysis of the data shows that the water of the Northern Urtabulok PPD is
distinguished by its exceptional hardness (505.0 mg-eq/l), the composition of
mineral salt precipitates (according to the ratio of the sum of cations and anions,
%-eq/l: Na
+
=32.5; Ca
2+
= 14.0; Mg
2+
= 3.5, Cl
-
= 49.0; SO4
2-
=1.0) and the content of
mechanical impurities and hydrogen sulfide.
The reaction of the chlorine-containing residue with alkanolamines and
soapstock was carried out in the following sequence: in a 250 ml round-bottom
flask with a solution and upon heating, monoethanolamine and potassium
hydroxide in a 1:1 mol ratio. The mixture was heated while stirring until
potassium hydroxide dissolved at a temperature of 75 °C. The resulting solution
was cooled to room temperature. A small portion of the chlorine-containing
residue during cooling was poured into the flask while constantly stirring, as this
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reaction is highly exothermic. As a result, diaminodiethyl ether of ethylene glycol
and potassium chloride were formed. Next, dietyl ether was added to the resulting
product (as a solvent), resulting in the precipitation of potassium chloride, which
we separated by filtration; the ether was distilled (tboil C
4
H
10
O = 34.6 °C).
Calculated amounts of soapstock - a secondary product of oil and fat plants - were
added to the resulting diamine. During the reaction, a mixture of β-
aminodiethylethyoxy-β-carboxamide of carbonic acids and glycerin is formed.
Glycerin was separated from the test substance using a separating funnel. The
mixture of β-aminodielethyoxy-β-carboxamide of carboxylic acids was
conventionally named (IngXO-DB) - a light yellow oily liquid with a pungent odor:
refractive index -1.469; boiling point - 290 °C; density - 0.9139 g/cm
3
.
A chlorine-containing waste generated in the vinyl chloride production at a
rate of 4500 t/year and not finding proper application was used as a raw material
source. Analysis of the composition of the chlorine-containing waste shows that
the product consists of a mixture of 32 products, mainly 1,1-dichloroethane, vinyl
chloride, acetaldehyde, and dichloroethylene.
Fig.1. Chromium-mass initial chlorine-containing waste
1 (0.091) benzene; 2 (0.943) Chlorethylene; 3 (1.014) chloroprene; 4 (1.137)
3-chloropropene; 5 (1.257) 1,1-dichloroethane; 6 (1.325) chloroprene; 7 (1.423)
2,2-dichloropropane; 8 (1.625) 1,2-dichloroethylene; 9 (1.760) 3-chloro-2-
methylpropene; 10 (1.948) 1,3-chlorocyclopentene; 11 (2.074) heptane; 12
(2.191) 5.5-dimethylhexane; 13 (2.345) methylcyclohexane; 14 (2.499)
ethylcyclohexane; 15 (3.036) 2-chloro-1,3-butadiene; 16 (3.179) 1,1,2-
trichloroethane; 17 (3.291) 1,3-dichlor-2-butene; 18 (4.105) 3-chloro-2-
chloropentane; 19 (4.199) 1,3-dichlorobutane; 20 (4.722) 3-chloro-2-methyl-1-
propene; 21 (4.845) 1-chloro-2-methylcyclopropane; 22 (5.105) chlorobenzene;
23 (5.262) non-identified substance; 24 (5.402) 3-methyl-1-chlorobutane; 25
(5.542) ethylbenzene; 26 (5.807) 3,5,6-trichloro-2-pyridinium acetone; 27
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00 11.00 12.00 13.00
2e+07
4e+07
6e+07
8e+07
1e+08
1.2e+08
1.4e+08
1.6e+08
Time-->
Abundance
TIC: v-26052021-isxod1DA.D\ data.cdf
0.091
0.943
1.014
1.137
1.257
1.325
1.423
1.625
1.760
1.948
2.074
2.191
2.345
2.499
3.036
3.179
3.291 4.105
4.199
4.722
4.845
5.105
5.262
5.402
5.542
5.807 6.878 7.867
8.481
9.184
11.780
12.180
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(6.878) benzaldehydehydrazone; 28 (7.867) dihydrotoluene; 29 (8.481)
2,2,4,6,6-pentamethylheptene; 30 (9.184) 2 (1H) -pyridinone; 31 (11.780) 1,3-
bromochlorocyclobutane; 32 (12.180) 1,3-dichlor-2-butane.
Table 2-7 presents data on the corrosion rate of St.3 steel and the protective
effect of the "INHO-BD" inhibitor Z depending on the H
2
S concentration in a
solution with 50 g/l NaCl, obtained as a result of 24 and 240 hours of testing. The
protective effect Z increases with increasing H
2
S concentration in the solution and
already at an inhibitor content of 100 mg/l, a corrosion rate close to 0.04 g/
(m
2
/h) is achieved (Table 1), which corresponds to a value of about 0.05
mm/year, which is proposed as a standard for characterizing the sufficient
effectiveness of the inhibitor.
Table 2
The influence of H
2
S concentration in the solution on the corrosion rate of
steel St.3 and the protective effect of the "INHO-BD" inhibitor, according to 24-
hour tests.
C
H2S
mg/l
50 mg/l
100 mg/l
Single mg/l
К, g/m
2
h
Z, %
К, g/m
2
h
Z, %
0
0,18
-
0,40
-
10
0,07
59
0,07
83
20
0,06
67
0,06
86
30
0,04
76
0,04
90
40
0,03
85
0,02
94
The investigated inhibitor is sufficiently effective at excess CO2 pressure equal to
1 and 2 atm. (Table 2). In the presence of H2S (100 mg/l) and CO2 (1 excess
atmosphere), the inhibitor at a concentration of 200 mg/l shows somewhat higher
effectiveness compared to pure carbon dioxide media (3-table).
Table 3
The corrosion rate of steel and the protective effect of the "INHO-BD" inhibitor at
an excess CO
2
pressure equal to 1 atm (numerator) and 2 atm (denominator)
(Experiment duration 24 hours)
Сinh. mg/l
0
10
20
30
40
К, g/m
2
h
200
,
0
181
,
0
091
,
0
075
,
0
076
,
0
068
,
0
050
,
0
046
,
0
041
,
0
036
,
0
E, %
-
73
77
80
81
92
92
97
97
Table 4
Dependence of the corrosion rate of steel and the protective effect of the "INHO-
BD" inhibitor on its concentration in solution in the presence of H
2
S (100 mg/l)
and CO
2
(1 sample) simultaneously, according to 24-hour tests.
Сinh. mg/l
0
10
20
30
40
К, g/m
2
h
0,291
0,106
0,084
0,050
0,031
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E, %
0
63
71
83
89
Below are the results of 10-day corrosion tests.
Table 5
The influence of H
2
S concentration in the solution on the corrosion rate of steel
St.3 and the protective effect of the "INHO-BD" inhibitor, according to 240-hour
tests.
C
H2S
mg/l
50
100
Сinh. mg/l
К, g/m
2
h
Z, %
К, g/m
2
h
Z, %
0
0.040
-
0,100
-
25
0,028
30
0,034
66
50
0,013
68
0,017
83
100
0,012
69
0,013
87
200
0,009
77
0,001
90
Table 6
The corrosion rate of steel and the protective effect of the "INHO-BD" inhibitor
at an excess CO
2
pressure equal to 1 atm (numerator) and 2 atm (denominator)
according to 240-hour tests.
Сinh. mg/l
0
10
20
30
40
К, g/m
2
h
071
,
0
067
,
0
046
,
0
041
,
0
041
,
0
036
,
0
035
,
0
030
,
0
027
,
0
024
,
0
E, %
-
53
57
61
66
70
77
84
88
Table 7
Dependence of the corrosion rate of steel and the protective effect of the "INHO-
BD" inhibitor on its concentration in solution in the presence of H2S (100 mg/l)
and CO
2
(1 sample atm) simultaneously, according to 240-hour tests.
Сinh. mg/l
0
10
20
30
40
К, g/m
2
h
0,079
0,037
0,030
0,026
0,004
E, %
-
62
72
77
97
Comparison of the results of daily and ten-day corrosion tests shows that the
corrosion rate of steel decreases over time in both inhibited and uninhibited
solutions, and the increase in H
2
S concentration contributes to an increase in the
protective effect of the inhibitor during both test durations.
The combined presence of H
2
S and CO
2
causes an increase in inhibitor Z
compared to pure carbon dioxide environments. The values of the inhibitor's
protective effect, according to ten-day tests, were noticeably and reliably lower
compared to the daily exposure of the samples.
The corrosion rate of steel is higher in solutions containing both hydrogen
sulfide and carbon dioxide than in solutions containing hydrogen sulfide of the
same concentration. Obviously, this is due to the acidification of the medium in
the presence of CO
2
.
Thus, the inhibitor "INHO-BD" allows achieving a corrosion rate of 0.04 g/
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(m
2
h) in a highly mineralized (50 g/l NaCl) hydrogen sulfide-containing medium
during daily testing, only at a concentration of at least 20 mg/l. However, with an
increase in the duration of the tests by an order of magnitude, a similar corrosion
rate is observed already at an inhibitor concentration of 25 mg/l. This is also
characteristic of carbon dioxide and hydrogen sulfide-carbon dioxide solutions.
Thus, the "INHO-BD" inhibitor in the composition with Zn-OEDF allows
achieving a corrosion rate of about 2 g/ (m
2
h) in a highly mineralized hydrogen
sulfide-containing medium during daily tests, only at a concentration of at least 6
mg/l. However, with an increase in the duration of the tests by an order of
magnitude, a similar corrosion rate is observed already at an inhibitor
concentration of 10 mg/l. This is also characteristic of carbon dioxide and
hydrogen sulfide-carbon dioxide solutions.
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