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CHEMICAL PROBLEMS 2018 no. 3 (16) ISSN 2221-8688 343
UDK 632.953.2
SYNTHESIS AND RESEARCH INTO ANTICORROSION AND BACTERICIDE PROPERTIES OF CHLORINE-CONTAINING IMIDAZOLINE COMPLEXES OF
DISTILLATED NATURAL OIL ACIDS
N.A. Mammadova, S.A. Mamedkhanova
Azerbaijan State Oil and Industry Universityj 20, Azadliq ave., AZ1010, Baku; e-mail: n.a.mamedova@inbox.ru
The imidazoline complexes obtained by reaction of distillated natural oil acids (NOA) with diethylenetriamin (DETA) have been synthesized. The chlorine-containing complexes of NOA were synthesized on the basis of obtained imidazoline, their physio-chemical characteristics and structure proved true by IR-and NMR spectrums data. The properties of chlorine-containing imidazoline complexes of NOA as inhibitors of H2S- and CO2-, bio-corrosion have been studied. The tests showed that CO2- and H2S- corrosions of the complexes protect a metal surface up to 95100%. The effect of the influence of synthesized complexes on life activity of sulphate-reducing bacteriums (SRB) in three concentrations at 300 C temperature during 15 days revealed that even at low concentrations these complexes may be recommended as high-effective inhibitors to oppose metal biocorrosion.
Keywords: corrosion, biodamage, distillated natural oil acids, imidazolines, inhibitors, sulphate-reducing bacteriums
The use of oilfield equipment is accompanied by various difficulties arising from biostate of charge, carbonic acid and hydrogen sulphide corrosion [1-3], etc. To control this effect, experts apply inhibitors of corrosion based on the basis of organic compounds with atoms of nitrogen, sulphur, oxygen and double bonds to thus favor
absorption on metal surface [4]. It revealed that some nitrongen-containing derivatives of oil acids are C02 - corrosion [5,6].
The article deals with the results of investigations on working out CO2- H2O -and bio-corrosion on the basis of imidazoline chlorine-containing derivatives of natural oil acids (NOA) with diethylenetriamin (DETA).
EXPERIMENTAL PART
To synthesize chloroderivatives of NOA, the natural oil acids of "Karvan-L" diethylentriamin (DETA) (company "Kazanorgsyntensi," Russia), allyl chloride (Moscow company "Component Reactant", Russia) were used while the propyl chloroester of NOA was synthesized by authors of the article. The all reagents were used without any purification.
The structures of the obtained complex compounds were proved out by IR spectral analysis. Also, IR-spectrum of samples were registered on Fourier microscope LUMOS (firm BRUKER Germany) within wave frequency 600-4000 sm-1.
NMR1H spectrums were registered on Bruker Avance (Germany) II+300 (Ultra Shield ™ Magnet) 300 MHz, solvent-CD3COOCD3, chemical shifts are cited conformably TMS.
Some physical-chemical indices of complex compounds obtained on the basis of Baku natural oil acids were established. Crystallization temperature was established by
2 0
standard - 5066-91, index of refraction nD on refractometer IRF-22 N700060, relative density (d|°) by standard 3900-2000.
Synthesis of imidazoline of NOA. The 0.1 mol of NOA was put in a round-bottom-four-neck flask supplied with a mixer,
thermometer, opposite cooler and dropping funnel, then mixed and heated up to 80-900C temperature and DETA was discharged by means of dropping funnel within 1.5 hours. The initial compounds were given by mole correlation equal 1:1. During synthesis process the temperature was raised up to 2400C and maintained for 3.5 hours. It should be noted that at1300C temperature the amino amid of NOA was obtained as intermediate compound. Mixing continued until the temperature fell to 50-600C. It revealed that through the synthesis of imidazoline derivative of NOA on the basis of DETA a greater quantity of solid substances were formed with yield up to 90% mas synthesis of the chloride complex N-allyl imidazoline NOA (chloride of complex ).
Synthesis of the chloride of N-allyl
imidazoline complex of NOA (Chloride of complex I). The imidazaline of NOA and allylchloride were used as initial compounds in mol correlation 1:1. The reaction proceeded at 40-500C by mixing within 3-3.5 hours in the presence of solvent isopropyl alcohol. A yield of chlorine-containing imidazoline derivative of NOA is 95% mass.
Synthesis of chloride complex N-propyl naphtenate imidazoline of NOA (Chloride of complex II). The reaction proceeded on the basis of above-mentioned methods but at a temperature of 80-900C (a boiling point of isopropyl alcohol) during 3 hours. The imidazoline of NOA and propyl chloride ester of NOA were taken as initial compounds. Complex compounds obtained with 97% mass of yield.
RESULTS AND THEIR DISCUSSION
The synthesis of imidazoline of NOA proceeds by the interaction of NOA with DETA according to the scheme below:
r- + h2n- ch2-ch2-nh-ch2- ch- nh2 -► r-c<
13CP
-h2o'
NH- CH2 — CH2 — NH — CH2 — CH2—NH2
240
P
-H2O
¿N- CH2
-^R-Cv I 2
N— CH2 i 2
CH2 — CH2-NH2 where, R -mixture of alkyl, izoalkyl and naphtenic radicals
The synthesis of chlorine-containing imidazoline of NOA with chlorine-containing imidazoline complexes of distillated natural oil products according to the scheme below: acids proceeds by the interaction of
+ CH2= CHCH2Cl
kn:
n _ chj
ch,
^n _ ch2 i 2
^ n — ch2
CH
.ch,
nh2
Ch2 _ch2_ Nh2
H 2^=CH—CH2
Cl"
RCOOCH2CH2CH2Cl
^.n _ ch2 ^^ i 2
- n — ch2 + CH2 _ch2_ nh, rcooch2ch2Ch2
CT
-2
+
Note that the synthesized products spectroscopy method. These are followed by were identified by IR and 1H NMR- bands of absorption in the IR-spectrum
imidazoline of NOA: deformative (1552,1607 sm-1) and valence (3279 sm-1) vibrations of N-H bond in group NH2, deformative vibrations (2923,1454, 2813, 2853,1375 sm-1) C-H bond
Resonance signals inherent in NOA (CH3, CH2, aromatic and naphthenic cycles) are observed in a sample of imidazoline of NOA of the proton spectrum. The chemical shifts at 5 = 0.90 and 1.35 m.d. correspond to CH3 and CH2 resonance signals for alkyl groups, in the range 5 = 1.5-1.8 m.d. for the
of CH2, CH3 - groups, deformative vibrations (1010, 1138, 1272 sm-1) C-N bond and deformative vibrations (1655 sm-1) C= N bond (Fig1).
naphthenic ring. The resonance signals corresponding to amidoamines, in the magnetic field region 5 = 2.3 - 3.10 m.d, are characteristic for - CH2 - NH2 groups, and at 5 = 2.0-2.2 m.d. is characteristic for NH2 groups, at 5 = 3.30-3.60 m.d. identified by signals related to the ethyl groups (fig.2).
Fig 2. 1H-NMR of imidazoline of NOA
Next comes the following band absorption in IR-spectrum Chloride of complex I: valence (2870, 2925, 2966 sm-1) and deformative vibrations (1377, 1460 sm-1) of C-H bond of CH2 , CH3 groups; deformation (951, 1549 sm-1) vibrations of N-H bond in groups NH2; valence(1105, 1129, 1160 sm-1)vibrations C-N
bond, valence(1645 sm-1) vibrations C=N bond, deformative (1404 sm-1) vibrations of CH2 group wide band N +, deformativ (922, 977 sm-1) vibrations of C=C bond in a-position and valence (3048 sm-1) vibrations of =CH2 groups(fig3).
» st - g a - .1 s - e e - 1 1 n /" s 1 / I / • ii \<s 1 5 Vi i is ? I - y i V / " S Si u/ p — rf B a s 9 g "I
3 on g
350q 3000 2500 2qoo wavenumber cm-1 1soo 1000
Fig 1. IR Spectrum of imidazoline of NOA
Fig 3. IR Spectrum of chloride of complex I
There is a band absorption in IR-spectrum chloride of complex II as follows: pendular (724 sm-1) oscillations of C-H bond of CH2, deformative (1457, 1460 sm-1) and valence(2923, 2955 sm-1) vibrations of C-H bond of CH2 group, deformative(2923,2955 sm-1) vibrations of C-H bond of CH3; valence
(1378 sm-1) for C=O bond of ester and (1647 sm-1) vibrations of C-N bond, deformation (952 sm-1) vibrations of N-H bond in groups NH2; valence (1129, 1160 sm-1) vibrations C-
N bond, deformative (1547 sm-1) and valence (3291 sm-1)vibrations of C-N bound NH+, NH, NH2 groups (fig 4).
Fig 4. IR Spectrum chloride of complex II
Physio-chemical parameters of synthesized chlorine-containing imidazoline complexes are shown in Table 1.
Table 1. Physio-chemical parameters of synthesized products
Name of complex compounds Correlation of complexes df kq/m3 < Freezing point, 0C Yield , %
Imidazoline of NO A 1:1 1086 1.2340 17 89.9
Chloride of complex N-allyl imidazoline of NO A (Chloride of complex I) 1:1 1105 1.2160 - 95
Chloride complex N-propyl
naphtenate imidazoline of NOA 1:1 1045 1.1885 - 97
(Chloride of complex II).
Antibacterial properties of synthesized imidazoline complexes of NOA. The
influence of synthesized chlorine-containing imidazolin complexes of NOA on the vital activity of SRB. SRB's 1143 strain was tested. Sterilized test tubes with 20 ml volume were used in the experiment [6]. Bactericidal effect of the reagents mainly manifested itself during 15 days and then examined on the basis of calculation of the generated H2S content. Note that H2S was determined iodometrically. The
Special additives were put into the nutrient medium for the development of SRB. These additions have the following composition: 5% solution of FeSO47H2O in 2% solution of hydrochloric acid, 5% aqueous solution of NaHCO3, 1% of crystalline
According to Table 3, when SRB affects on chloride of complex II in correlation 1:1 with concentrations of 15, 75, 150 mq/l, no
water was chosen as a solvent for the complexes which dissolved well to generate transparent solutions with 1% concentration. SRB are obligate anaerobic bacteriums that dissimilate sulphates into hydrogen sulfide (H2S). Medium "Postgate - B" is more effective nutrient medium for SRB development. The composition of nutrient medium "Postgate -B" is shown in Table 2. The pH of the medium should be within 7.07.5.
Na2S9H2O is in the 1% aqueous solution of Na2CO3.
The influence of the dependence of chlorine-containing imidazoline complexes of NOA at concentrations of 15, 75, 150 on the growth of the bacterium is shown in Table 3.
H2S formation is observed because this complex at all concentration displays a 100% bactericid effect to completely suppress the
Table 2. Composition of feeding medium "Postgate-B"
№ Name of compounds Gramme № Name of compounds Gramme
1 Potassium salt of dihydrophosphate acid 0.5 4 Magnesium sulphate 2.0
2 Ammonia chloride 1.0 5 Sodium lactate 3.5
3 Calcium sulphate 1.0 6 Sodium chloride 2.0
Table 3. The effect of protecting chlorine-containing imidazoline complexes of NOA.
„ ... , Correlation of Conditional name , complexes Concentration of comp exes, mq/l
15 75 150
Amount of forming H2S, mg/l
Chloride of complex I 1:1 80 40 -
Chloride of complex II 1:1 - - -
Medium 1 "Postgate-B" 24-32
Medium 2 "Postgate-B" and SRB 275
Corrosion protection of complexes %
Chloride of complex I 1:1 70,9 85,4 100
Chloride of complex II 1:1 100 100 100
growth of SRB. Chloride of complex I exerts biostate action, and at 75 mg/l it demonstrates biocide action and suppresses the activity of SRB. At concentration of 150 mg/l it shows 100% bactericide effect to suppress the growth of SRB.
Anticorrosion properties of synthesized complexes. The ACM GL was used to study the kinetics of the CO2 corrosion process. The process is carried out at a temperature of 500
Table 4. Effect of complex solul
°C, with the participation of an electrode of low-carbon steel C1018. During a 20-hour test, the corrosion current and the loss of metal and corrosion rates (mm/year) were calculated automatically every 15 minutes in the research. The obtained chlorine-containing imidazoline complexes of NOA were tested as corrosion inhibitors at 100 ppm. The effect of complex solutions on the C02 corrosion process is shown in Table 4.
ns on the C02 corrosion process
Solution numbers Corrosion current, mA/c Corrosion rate, mm/year Total metal Potential (mV)
Chloride of complex I 0.0233 0.2702 0.0006 587.6
Chloride of complex II 0.0158 0.1833 0.0007 619.9
Without inhibitors 0.3406 3.9474 0.0067 -689.6
At the turn of 20 hours, the effect of reached 95.35% and 93.14% mass (Fig.5) corrosion protection of these chlorine- respectively. containing imidazoline complexes of NOA
4,5
0 2 4 6 S 10 12 14 16 IS 20
Fig. 5. The influence of chlorine-containing imidazoline complexes of NOA on the corrosion kinetics of CO2 in a 1% aqueous solution of NaCl saturated with CO2 at 100 ppm.
The effect of chlorine-containing imidazoline complexes of NOA on H2S corrosion was analyzed as well. The two-phase systems of water: kerosene in 9: 1 ratio was used in the investigation. The water was saturated with H2S to 500 mg / l. The medium was mixed by a magnetic mixer. The
experiment lasted for 5 hours. The steel plates for 3 hours. The experiments showed that the best indications proved to be chloride of complex I at a concentration of 5, 10, 15 ppm showing respectively 92, 95.99 and 100 %, chloride of complex II at all concentrations showed 100% protection against H2S
corrosion which makes it possible to and bactericidal properties of recommend them as an H2S corrosion inhibitor chlorinecontaining complexes I and II. (Tab.5). Table 4 provides data on inhibiting
Table 4. Comparative analysis of inhibiting and bactericidal properties of complexes
Name of complex Corrosion protection Corrosion protection Influence
from H2S from CO2 on SRB
Min. Effect Min. Min. Effect Min.
consentr pro consen- consentrat pro consen-
ation tection tration ion mq/l tection tration
mq/l % mq/l % mq/l
Chloride of complex N-allyl 5 92 100 95,35 15 70,9
imidazoline of NOA 10 95,99 75 85,4
(Chloride of complex I) 15 100 150 100
Chloride complex N-propyl 5 100 100 93,14 15 100
naphtenate imidazoline of 10 100 75 100
NOA(Chloride of complex II). 15 100 150 100
RESULTS
The imidazolines NOA obtained on the basis of natural oil acids with diethylenetriamine were synthesized. The chlorine-containing imidazoline complexes of NOA were obtained on the basis of synthesized imidazoline NOA having been tested as inhibitors: 1) with CO2 corrosion (100 ppm) the chlorine-containing imidazoline complexes of NOA protect the metal surface at 93.14 and 95.35%, 2) with H2S corrosion (5, 10, 15 ppm) the chloride of complex N-allyl imidazoline of NOA protects the metal surface respectively at 92, 95.99 and 100%; Chloride
complex N-propyl naphtenate imidazoline of NOA (5 ppm) protects the metal surface against H2S corrosion by 100%. The physicochemical characteristics and the effect of the synthesized compounds on the activity of sulfate-reducing bacteria in three concentrations at 300C for 15 days were also studied. It found that the chloride complex N-propyl naphtenate imidazoline of NOA at low concentrations (15ppm) has higher antibacterial properties and can be recommended as a highly effective inhibitor against bio-corrosion of metals.
REFERENCES
1.Tributsch H., Rojas Chapana J.A. Metal sulfide semiconductor electrochemical mechanisms inducted by bacterial activity. Electrochim. Acta. 2000, vol. 45, pp. 47054716.
2. Miranda E., Bethencourt M., Botana F.J., Cano M.J., Sanchez-Amaya J.M., Corzo A., Olivier B. Biocorrosion of carbon steel alloys by an hydrogentrophic sulphate-reducing bacterium Desulfovibrio capillatus isolated from a Mexican oil field separator. Corrosion Science. 2006, vol. 48, pp. 24172431.
3. Abbasov B.M., Jabrailzade Sh.Z., Mursalov
N.i. and other. Sulfonous distillates of diesel fuel as corrosion inhibitors and bactericides. Journal of Natural and Technical Sciences. 2010, no. 3 (47), pp. 60-64.
4. Abbasov V.M., Haney M. Abd El-Latef, Aliyeva L.I. et al. Evalution of new complex surfactants based on vegetable oil as corrosion inhibitors for midl steeel in CO2 saturated 1% NaCI solution. Journal of Materials Physics and Chemistry. 2013, no. 2, pp. 19-26.
5. Abbasov V.M., Rzayeva N.Sh., Talybov A.G. Synthesis and study of sulfate derivative of N-cyclohexylamides of oleic acid as an inhibitors of CO2 corrosion. /13 th Ibn Sina
International Conference on Pure and Applied Heterocyclic Chemistry «Heterocyclic Chemistry for Sustainable Future». Hurgada, Egypt, 14-17 february 2015, p. 211.
6.Kuznetsov Y.I. Physio-chemical aspects of the inhibition of corrosion of metals in water governmental solution. Russian Chemical Reviews. 2004, vol. 73, no.1, pp.79-93.
СИНТЕЗ И ИССЛЕДОВАНИЕ АНТИКОРРОЗИОННЫХ И БАКТЕРИЦИДНЫХ СВОЙСТВ ХЛОРСОДЕРЖАЩИХ ИМИДАЗОЛИНОВЫХ КОМПЛЕКСОВ ПРИРОДНЫХ НЕФТЯНЫХ
КИСЛОТ
Н.А. Мамедова, С.А. Мамедханова
Азербайджанский Государственный Университет Нефти и Промышленности, Az 1010, г. Баку, пр Азадлыг 20, e-mail: n. a. mamedova@inbox. ru
Синтезированы имидазолиновые комплексы, полученные реакцией дистиллированных природных нефтяных кислот (ПНК) с диэтилентриамином (ДЭТА). На основе полученного имидазолина синтезированы хлорсодержащие комплексы ПНК, определены их физико-химические характеристики; строение подтверждено данными ИК и Н'ЯМР спектров. Изучены свойства хлорсодержащих имидазолиновых комплексов ПНК в качестве ингибиторов H2S - , СО2- и биокоррозий. Испытания показали, что при СО2- и Н2Б- коррозиях комплексы защищают поверхность металла до 95-100%. Эффект воздействия синтезированных комплексов на жизнедеятельность сульфатвосстанавливающих бактерий (СВБ) в трех концентрациях при 300С в течение 15 суток выявил, что даже при низких концентрациях комплексы могут быть рекомендованы в качестве высокоэффективных ингибиторов против биокоррозии металлов. Ключевые слова: коррозия, биоповреждение, дистиллированные природные нефтяные кислоты, имидазолины,ингибиторы, сульфатвосстанавливающие бактерии.
TBBii NEFT TUR§ULARININ XLORTBRKiBLi iMiDAZOLiN KOMPLEKSLdRiNiN SiNTEZi, ONLARINKORROZiYAYA QAR§I Yd BAKTERiSiD XASSdLdRiNiN TBDQiQi
N.B. Mzmmzdova, S.d. Mzmmzdxanova
Azdrbaycan Dövldt Neft vd Sdnaye Universiteti AZ 1010, Azadliqpr., 20; e-mail: n.a.mamedova@inbox.ru
Tdbii neft tur^ularinin (TNT) dietilentriaminld reaksiya ndticdsindd imidazolin komplekshr sintez edilmi^dir. Alinan imidazolin komplekshr dsasinda xlortdrkibli komplekshr sintez olunmuonlarin fiziki-kimydvi xassdldri müdyydn olunmuqurulu^lari iQ- vd NMR- spektral analizhri ih tdsdiq olunmu^dur. TNT-nin xlortdrkibli imidazolin kompleksldri hidrogen sufid, karbon qazi vd biokorroziyaya qar^i inhibitor kimi xassdldri tddqiq olunmu^dur. Tddqiqatlar ndticdsindd müdyydn edilmi^dir ki, karbon qazi vd hidrogensulfid mühitindd korroziya zamani bu komplekshr metal sdthini 95-100%-d qdddr mühafizd edirldr, sulfatreduksiyaedici bakteriyalarin hdyat fdaliyydtind isd dn a§agi qatiliqda, 300C temperaturda, 15 sutka drzindd mdhvedici tdsir göstdrmi§ vd metallarin biokorroziyasina qar^i yüksdk effektiv inhibitor kimi tdklif olunmu^dur.
Agar sözldr: korroziya, biozdddldnmd, tdbii neft tur^ulari, imidazolin, inhibitor, sulfatreduksiyaedici bakteriyalar
