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KÎMYA PROBLEML9RÎ № 4 2017 ISSN 2221-8688
UDC 665.753.4:546.22:547.781.785
EFFECT OF iNORGANiC COMPLEXES OF ÎMiDAZOLÎNE BASED ON SYNTHETiC PETROLEUM ACiDS AND TRiETHYLENTETRAMiN AGAiNST
CARBON DIOXIDE CORROSiON
V.M. Abbasov, E.H. Mamadbayli, D.B. Agamaliyeva, L.A. Mahmudova, F.F.Tahirova, V.H. Babayeva, Kh.A. Abbasova
Y.H. Mamedaliyev Institute of Petrochemical Processes
National Academy of Sciences of Azerbaijan. Khojali pr., 30, AZ1025, Baku, Azerbaijan Republic e-mail: durna.agamaliyeva@mail.ru
Imidazoline derivatives have been synthesized on the basis of synthetic petroleum acids and triethylentetramine. Complexes were prepared from the above-stated compounds and HCl in the ratio 1:2, 1:3. Note that 20% solutions of the complexes were prepared in aqueous isopropyl alcohol. The kinetic effect of steel corrosion in CO2 -saturated 1% NaCl solution has been examined by ACM Gill AC potentiometer. It revealed that imidazoline derivative complexes based on the SPA and TETA with HCl in the molar ratio 1:2 at concentration of 25 mg/l had corrosion protection 87.0%, at concentration of 50 mg/l - 96.4% and at concentration 100 mg/l - 97.1%; however, in the mole ratio of 1:3 the complex reveals its best results - 93.8, 97.8 and 98.4%. Keywords: corrosion inhibitor, synthetic petroleum acids, oxidation, triethylentetramin, imidazoline
iNTRODUCTiON
Corrosion of metal constructions, specifically oil and gas industry equipment, incurs great losses to all spheres of national economy. This is due to highly aggressive components of the said equipment and its operation. On the other hand, corrosion consequences in all spheres of industry lead to unscheduled shutdowns. As a result, it negatively affects economic indices of oil and gas industry.
Manufacture of equipment from anticorrosion materials does not always secure its reliability and durability. That's why other methods have to be used in corrosion protection matters.
A widely used method to reduce aggressiveness of corrosion components is the use of inhibitors [1-3].
Key requirements include as follows: inhibitors are to be obtained through the use of
available raw material, have multifunction effect and be cheap. Worthy of note among inhibitors which comply with current requirements are nitrogen-containing organic compounds obtained on the basis of synthetic (SPA) and natural petroleum acids of major importance. In this respect, it is very important to use SPA which is obtained from catalytic oxidation of naphthenic-paraffinic hydrocarbons and new hydrocarbons in liquidphase obtained from Azerbaijani oil [4-7]. Thus, for SPA synthesis there were used fractional reserves that are available in our country. On the other hand, unlike derivatives of oil acids, derivatives of these acids their freezing temperatures are much lower.
The article deals with the production of new inhibitors which are highly effective in CO2 mediums to comply with the above-mentioned requirements.
EXPERiMENTAL PART
Note that SPA has been used for synthesis of highly effective corrosion inhibitors. To obtain SPA, Azerbaijani oil of de-aromatized boiling fraction with boiling interval of 250-3500C has been used. The process of dearomatization was carried out through the use of sulfurization. Naphthenic-paraffinic hydrocarbons were oxidized in liquid-phase with oxygen of air in the presence
of catalyst of salts of natural oil acids. The process has been carried out within 6 hours at a temperature of 135 0C in a special reactor.
Synthesis of SPA derivatives and tiethylentetramine (TETA) gets through two stages. In the first stage, there was obtained an amid compound on the basis of SPA and TETA, in the second stage - imidazoline derivatives:
^ 130o
r— + h2nch2ch2(nhch2ch2)2ch2ch2nh2___
_^ r_c^ ,, ..o
xnh— ch2ch^(|nhch2ch^ch2 ch2nh2 _2jh0°»
^n — ch2 — ^c^" i 2
ch2
Ch2 ch2nh ch2 ch2 nh2
The structure of the synthesized imidazoline was explored through IR and NMR spectroscopy.
- CH2 ch2
+HCl
Ch2ch2 nhch ch2 nh9
Complexes based on the obtained imidazolines with HCl were synthesized under normal conditions:
+
- ^
^n _ch9
Chch2nhch2ch2nh
cl-
Complexes were prepared from the said compounds and HCl in the ratio 1:2 (sample 1), 1:3 (sample 2). Note that 20% solution of the complexes came as a result of the use of
aqueous isopropyl alcohol. The kinetic effect on steel corrosion in Co2-saturated 1% NaCl solution was analyzed by ACM Gill AC potentiometer.
RESULTS
One of the effective methods of struggle against carbon-dioxide corrosion is the use of inhibitors. Types of corrosion inhibitors are not a lot of. Amines, amides, imidazolines and salts of quaternary ammonium are used most frequently [9-11].
Note that the concentration 25, 50 and 100 mq/l of complexes have been analyzed
within 20 hours. At the same time, corrosion of steel samples was explored in the absence of corrosion inhibitor.
Fig. 1 shows that in the absence of inhibitor the corrosion rates become faster as time goes by. At concentration of 100 mg/l after 5 hours the protection effect increases from 93.8% to 98% after 20 hours of research:
Fig. 1. Dependence of corrosion rate upon time for steel in CO2-saturated 1% NaCl solution containing various and sample 1 at 50 0C.
Fig. 1 shows the effect of sample 1 on the corrosion rate of carbon steel in CO2 saturated 1% NaCl solution at a temperature of 500C.
-25 mq/l
■ 50 mq/l
• 1 00 mq/l
without I
Time(hour)
Fig 2. Dependence of corrosion rate upon time for mild steel in CO2-saturated 1% NaCl solution at various concentrations of sample 2 at a temperature of 50 0C.
Sample 2 at various concentrations in the CO2 medium was studied. At concentrations of 25 mq/l in sample 2 following 5 hours of research the corrosion effect grows from 92,3% to 93,8% after 20 hours of research; at concentration of 100 mq/l 5 hours of research a figures rises from 93,8% to 98,4 %. Fig. 2
shows the effect of sample 2 on the corrosion rate of carbon steel in CO2 saturated 1% NaCl solution at 50 0C.
Results of research into inhibitor effectiveness of synthesized complexes at various concentrations are shown at Table 1.
Table 1. Results of inhibitor effectiveness of complexes
Sam ple -1 Sam ple -2
Concentration, Time, Corrosion Protection Corrosion Protection
C, mq/l hour rate, effect, rate, effect,
P, Z, % P, Z, %
mm/year mm/year
Without 5 12.611 - 12.611 -
inhibitor 10 14.48 - 14.48 -
20 15.148 - 15.148 -
25 5 2.510 80.7 0.974 92.3
10 2.22 81.7 0.947 91.2
20 1.962 87.0 0.857 93.8
5 0.712 87.2 0.517 95.9
50 10 0.518 92.0 0.538 96.3
20 0.55164 96.4 0.588 97.8
5 1.065 91.6 0.318 93.8
100 10 0.617 95.7 0.423 95.0
20 0.440 98.1 0.295 98.4
Thus, protection complex in the various mole ratio at low concentrations grows with the rise ion mole share. Thus, sample 1 at concentration of 50 mq/l following 20 hours of research masde up 96,4%, for sample 2 it reached 97,8%. However, corrosion protection effect of samples at concentration of 100 mq/l following 20 hours of research changed insignificantly.
It should be noted that the kinetic effect of steel corrosion on the basis of imidazoline
obtained from SPA and TETA and SPA in 1% NaCl sdaturated with CO2 on the steel corrosion yields higher effect. Complexes based on imidazoline and HCl in the molar ratio 1:3 as compared with 1:2 molar ration are more exposed to chemisorption on the metal surface than in the ration 1:2, that's why protective films on the surface are more stable. For this reason, the complex is notable for higher corrosion protection effect than previous ones.
REFERENCES
1. Abbasov V.M., Aliyeva L.I., Efendiyeva L.M. Efficiency of imidazolines on the basis of oil acids in the condition of acid corrosion of steel. Praktika potivokorrozionnoj zashhity - Practice of Anticorrosive Protection 2012, no. 2 (64), pp. 38-41. (In Russian).
2. Abbasov V.M., Abd El-Lateef H.M., Aliyeva L.I. et all. Evaluation of new complex surfactants based on vegetable oils as corrosion inhibitors for mild steel in CO2 -saturated 1.0% NaCl solutions. Journal of materials Physics and Chemistry, 2013, vol. №2, pp. 19-26.
3. Quraishi M.A., Khan S. Thiadiazoles-A potential class of heterocyclic inhibitors for
prevention of mild steel corrosion in hydrochloric acid solution. Indian Journal of Chemical Technology, 2005, vol. 12, pp. 576581.
4. Cirinnova V.S., Miljkovic D.A., Repic S. Synthesis of Petroleum Acids by the Catalytic oxidation of Medium Distillates of Naphthenic Crude Oil. Neftehimiya -Petroleum Chemistry, 1992, 32 (6), pp. 448453. (In Russian).
5. Voloshin V F., Skopenko V.S. Voloshin V.V. Inhibition of electrochemical corrosion of steel in environments containing hydrogen sulfide. Visnik Pridniprovs'koï derzhavnoï akademiï budivnictva ta arhitekturi - Bulletin of Prydniprovs 'ka State Academy of
Civil Engineering and Architecture. 2011, № 1-2, pp. 14-18. (In Ukraine).
6. Abbasov V.M., Abd El-Lateef H.M., Aliyeva L.I. et all. Inhibitive effect of some natural napthenates as corrosion inhibitors on the corrosive performance of carbon steel in CO2 - saturated brine. International Journal of Scientific Research in Environmental Sciences (IJSRES), 2013, 1(8), pp. 166-178.
7. Malkovskii P.A., Zainullov M.R., Minkhairov M.F. et al. Oxidation of naphthenic hydrocarbons of senomanion condensate. Neftehimiya - Petroleum Chemistry, 2003, 43 (1), pp. 46-49. (In Russian).
8. Ismayilov I.T., Abd El-Lateef H.M., Abbasov V.M. et all. A novel sulfated fatty acid amides-based surfactants: synthesis and effect on the corrosion inhibition of carbon
steel in CO2 - saturated 1% NaCl solution. Advances in Materials and Corrosion, 2012, no. 1, pp. 22-29.
9. Afandiyeva L.M. Inorganic complexes of imidazoline derivatives based on synthetic oxy-, petroleum acids as corrosion Kimya problemleri - Chemical Problems. 2017, no.1, pp. 67-71. (In Azerbaijan)
10. Duzdaban Kh.R. Research into imidazoline and butyric acid-based complexes in carbon dioxide medium. Kimya problemleri - Chemical Problems. 2016, no.1, pp. 44-49. (In Azerbaijan).
11. Rzayeva N.Sh. Corrosion-preventing liquids based on organic complexes of imidazoline acids of sunflower oil. Kimya problemleri - Chemical Problems. 2016, no.4, pp. 400-404. (In Azerbaijan).
ВЛИЯНИЕ НЕОРГАНИЧЕСКИХ КОМПЛЕКСОВ ИМИДАЗОЛИНА, ПОЛУЧЕННЫХ НА ОСНОВЕ СИНТЕТИЧЕСКИХ НЕФТЯНЫХ КИСЛОТ И ТРИЭТИЛЕНТЕТРАМИНА, НА УГЛЕВОДОРОДНУЮ КОРРОЗИЮ
В.М. Аббасов, Э.Г. Мамедбейли, Д.Б. Агамалиева, Л.А. Махмудова, Ф.Ф. Тагирова, В.Х. Бабаева, Х.А. Аббасова
Институт Нефтехимических Процессов имени Ю.Г. Мамедалиева Национальной АН Азербайджана, 1025, Баку, пр.Ходжалы 30 e-mail: durna.agamaliyeva@mail.ru
Синтезированы производные имидазолина на основе синтетических нефтяных кислот и триэтилентетрамина. На основе этих соединений и HCl получены комплексы в соотношении 1:2 и 1:3. 20%-ный раствор комплексов приготовлен в водном изопропиловом спирте. Исследован кинетический эффект коррозии стали в 1% -ном растворе NaCl, насыщенном СО2, с помощью потенциометра ACM Gill AC. Было обнаружено, что комплексы имидазолиновых производных на основе СНК и TЭTA с HCl в молярном отношении 1: 2 при концентрации 25 мг/л проявляют защитный эффект от коррозии 87.0%, при концентрации 50 мг/л - 96.4% и 100 мг/л - 98.1%, а в случае комплекса при мольном соотношении 1: 3 наблюдаются лучшие результаты - 93.8, 97.8 и 98.4% соответственно.
Ключевые слова: коррозия, ингибитор, синтетические нефтяные кислоты, окисление, триэтилентетрамин, имидазолин.
SiNTETiK NEFT TURgULARI VO TRiETiLENTETRAMiN OSASINDA SiNTEZ OLUNMUg iMiDAZOLiNiN QEYRi-UZVi KOMPLEKSLORiNiN CO2 KORROZiYASINA
TOSiRi
V.M. Abbasov, E.H. M9mm9db9yli, D.B. Agamaliyeva, L.A. Mahmudova, F.F. Tahirova,
V.H. Babayeva, X.A. Abbasova
AMEA Y.H. Mammadaliyev adina Neft-Kimya Proseslari institutu, Az 1025 BakiXocaliprospekti,30; e-mail: durna.agamaliyeva@mail.ru
Sintetik neft tur§ulari va trietilentetramin asasinda imidazolin toramasi sintez edilmi§dir. Sintez olunmu§ imidazolin va HCl asasinda 1:2 va 1:3 nisbatlarinda komplekslar alinmi§dir. Komplekslarin 20 %-li mahlulu sulu izopropil spirtinda hazirlanmi§dir. CO2 ila doymu§ 1%-li NaCl mahlulunda poladin korroziyanin kinetik effekti ACM Gill AC markali potensiometrin vasitasila tadqiq olunmu§dur. Malum olmu§dur ki, 1:2 nisbatinda sintez olunmu§ imidazolinin kompleksi 25 mq/l konsentrasiyada korroziyaya qari§i 87.0 % inhibitor effektina malikdir, 50 mq/l -96.4% va 100 mq /l - 98.1%, lakin 1: 3 nisbatinda daha yax§i naticalar mu§ahida olunur -muvafiq olaraq inhibitor effekti 93.8, 97.8 va 98.4% olmu§dur.
Agar sozlw. korroziya, inhibitor, sintetik neft tur^usu, oksidla§ma, trietilentetramin, imidazolin.
Received 12.10.2017
