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Section 10. Chemistry
https://doi.org/10.29013/ESR-19-9.10-65-71
Ismayilov Ismayil Teyub, Doctor of Chemical Sciences, Chief technologist Academician Y. H. Mammadaliyev Institute of Petrochemical Processes of Azerbaijan National Academy of Sciences, Baku
Khamieva Gunay Habil, Chemist, Academician Y. H. Mammadaliyev Institute of Petrochemical Processes of Azerbaijan National Academy of Sciences, Baku
Abdullayeva Minaya Bilal, postdoctoral student of Petrochemistry, and chemical engineering department, Sumgait State University, Republic of Azerbaycan
Manafov Elmir Ali, Teacher, school-Lyceum № 6, Baku Aghayev Akbar Ali, Doctor of Chemical Sciences, professor, Head of Petrochemistry and chemical enginering department Sumgait State University, Republic of Azerbaijan
E-mail: [email protected]
SURFACTANTS BASED ON THE COTTONSEED OIL AS PROBLEM RESOLVING REAGENTS FOR ECOLOGICAL PROBLEMS OF OIL INDUSTRY
Abstract. The colloidal-chemical parameters, surface-active properties including interfacial tension of the Na+, K+, NH4+, NH3+-CH2-CH2-OH and NH2+- (CH2-CH2-OH) 2salts of sulphate-derivatives of higher carboxylic acids ethanolamides have been studied. These surfactants also investigated as inhibitors of hydrogen sulfide corrosion, petroleum-collecting and petroleum-dispersing reagents. The results showed that complex salts could be used as effective corrosion inhibitors and reagents for removing petroleum films from water surface.
Keywords: cottonseed oil, ethanolamides, surfactant, hydrogen sulfide corrosion inhibitors, oil slicks, petroleum-collecting, petroleum-dispersing.
The current stage of development of the oil and in the proportion of light non-sulphurous crude oil gas industry in the world is characterized by a decrease and gas condensate reserves in contrast to a signifi-
cant increase in the consumption of hydrocarbons. The increase in the proportion of oil and gas raw materials with a high content of organic sulfur compounds was noted in various oil-producing regions of the world. Features of the composition of high-sulfur oils are expressed in high content of total sulfur, toxic and corrosive hydrogen sulfide and mercaptans. They contribute to corrosion damage to equipment due to sulphide corrosion, which leads not only to great direct losses, but also to environmental problems, as oil and petroleum products spills at all stages of production, processing, storage and transportation, and posing a considerable threat to the surrounding and environment, especially to world water basin [1-4].
The fate of the oil which has got to the sea can't be described in all details. The oil which has got to a reservoir quickly spreads. Even the thinnest oil film isolates water from air oxygen, thereby reducing its aeration. Small fractions quickly evaporate, and remained turn into a stable water oil emulsion. As the hydrocarbons evaporate, density and viscosity of an oil film increase, the surface tension decreases and spreading stops. Waves and currents break a film into separate drops [5].
It is established that the final fate of oil in the sea is defined by activity of microorganisms. The microorganisms that exits in sea water first of all consume n-al-kanes, and then aromatic com-pounds. The complexity of composition of oil and oil products demands a variety of the microorganisms capable to attack both oil components, and metabolism products. Therefore oil is more effectively destroyed not by individual strains, but by a mixed bacterial population [6-8].
Also it is known that the World Ocean plow tankers which transport by sea of the produced oil. When a tanker has accident near the coast, sea birds perish, coastal flora and fauna suffers, beaches become covered by a layer of viscous oil. The emergency tanker is usually surrounded with bonds from floating hoses which interfere spreading of the oil slick and allow collecting the spilled oil by pumps [9-10].
Among methods against oil spills on the water surface, which has recently received widespread use,
rather is use of special chemical reagents that allow during a short period of time to liquidate film oil on a large surface of reservoirs. They constrain spreading of oil and collect it on the smaller square, promoting considerable reduction of the area of a flood and increase in thickness of a layer of a floating film of oil and oil product [11-14].
Authors [15] recognize that passages of oil, in particular, at crashes of tankers, occur systematically and application of a way at which oil spills are processed previously by special reagents is advisable. Under their action there is a coagulation of oil products to formation of dense floating agglomerates. The following stage is their removal from a reservoir surface.
Authors [16] have offered a way for cleaning of a water surface from oil pollution consisting in addition to surface oil films of small amounts surfactant like fatty acids, alkylsulphatic pitches, alkylamines and other connections of this class.
In this work results of research as inhibitors of hydrogen sulfide corrosion of anion surfactants synthesized by the author [17] on the basis of cottonseed oil, which show rather high activity collecting of oil spills on a surface of the water are presented.
Experimental
Cottonseed oil (purity 99.5%) was supplied by "Shirvan Oil Factory" (Azerbaijan). Monoethanol-amine (MEA) and diethanolamine (DEA) were used as reagents of the pure grade of Olaynen Factory of chemical reagents (Latvia). Ammonium hydroxide was from the Kazanorgsintez Joint Stock Com-pany (Russia). Sulfuric acid (96% wt solution) was product ofMoscow's Component-Reactant Joint Stock Company (Russia). Isopropyl alcohol (IPA) was used as an industrial product of the factory "Organic sythesis" (Azerbaijan). NaOH and KOH (pure) were the products of Merck (Germany). The Pyral-lahy, Balakhany and Naphtalane crude oils were obtained from different oil companies located in Azerbaijan. Fresh water and sea water from the Caspian sea with following p20 = 1.0098 g/mL and pH = 7.7 physico-chemical characteristics and contents of ions and other species
(g/kg): Na+ 2.99, K+ 0.09, Ca2+ 0.34, Mg2+ 0.70, Cl-5.18, SO42-2.98 were used in the experiments.
Measurements of the interfacial tension were carried out using deionized water to make the solutions. The solutions kept at the desired temperature were measured 45 s after transfer to the thermostated measuring dishes. The actual temperature within the dishes was controlled prior to and after the measurement by means of a thermocouple. Deviations from the desired temperature were ± 0.3 oC. The interfacial tension as a function ofconcentration was measured at 20 oC using a drop volume stalagmometer. Interfacial tension values from the three measurements varying by no more than 0.3mN/m were averaged and reported.
A study of influence on petroleum-collecting and dispersing properties of the synthesized compounds has been performed according to the following procedure. Into Petri dish 40 mL of water were placed and onto it 2 mL of petroleum was added. The formed petroleum slick has a thickness ~0.255 mm. After formation of the slick a necessary amount of surfactant 5.0% wt. aqueous solution was added to a thin film
о
1
R— C-OCH2
2 о I t°
R2—C-O-CH + 2 NH3 x(CH2CH2OH)x-
о I
3 II I
R3—C-O-CH?
of this petroleum on the surface of fresh water and the Caspian Sea water (separately) in Petri dishes. The maximum values of the petroleum collecting coefficient (K) are calculated using the formula K = So/S, where So is an area of the surface of initial petroleum film and S is an area of the surface of accumulated petroleum (as a thickened spot). Since the moment of the surfactant application observations are carried out with measurement of the spot surface area and determination ofthe K values at fixed time intervals. When the petroleum film is dispersed, the percentage of the water surface cleaning (Kd) is found at the appropriate times of measurements. Kd is calculated as the ratio of the surface area cleaned from the petroleum and the surface area of the initial petroleum slick [18].
Results and discussion
Synthesis of surfactants
On the basis of cottonseed oil and the nitrogen-containing bases as which used monoethanolamine and diethanolamine according to the following reactionary scheme surface-active sulphatederivative salts of highest carboxylic acids ethanolamides were synthesized:
O
O CH2—OH
I 2
2 R-C-NH2-x(CH2CH2OH)x+ R—C-O-CH
R - r1> r2> r3 - C17H35> C17H33> C17H31
CH2—OH
C17H29, C15H31, C13H27; X - 1-2; t0 - 120, 150;
O
R1_^CH2CH=CH|—(CH2)7-C—NH2-X(C2H4OH)X +
rH-CH^H^HWCH^-C-O-CH
L J m I
CH2-OH
O CH2-OH +2H2SO4 (20%), 60-70oC
о
R14cH2CHCH2^(CH2)7"C-NH2_x(C2H4OH)x L J n
OSO2OH
+
о CH2OH
I I 11 1
R^CH2CHCH^(CH2)rCOH + CH—OH
CH2-OH
l^CH2CH'CH2j-i
OSO2OH
R1 - C7H15, C4H9, CH3; m, n - 1-3;
^CH2C»CH^o
O
O
R^CH2CHCH^j—(CH2)7-C—NH2-X(C2H4OH)X 1) ' ---------------R^C^CHC^Hc^bC-N^-x^^OH^
OSO2OH
O
R^CH2CHCH^(CH2)^^OH
I- I J m
OSO2OH
L I J„ OSO2O-M
1) + NaOH (20%)
2) + KOH (20%)
3) + NH4OH (20%)
+
4) + NH2CH2CH2OH O
5) + NH(CH2CH2OH)2 R1"^CH2CH CH2 j"m(CH2)7_C-°-M
" OSO2O-M
M - 1) Na+, 2) K+, 3) NH4+, 4) N+H3CH2CH2OH, 5) N+H2(CH2CH2OH)2
+
Intermediate products of synthesis are characterized by physical and chemical indicators as acid and iodic number and also identified by IK-spectras [17]. Final pro-ducts-solids are generally viscous liquids and completely soluble in IPA and partially soluble in water, and also readily soluble in water: IPS mixture in different ratios. They marked as: CMI, CMII, CMIII, CMIV, CMV, CDI, CDII, CDm, CDIV and CDV C is the index as cottonseed oil, M - aminoly-sis of cottonseed oil, carried out in the presence of MEA, D - aminolysis of cottonseed oil, carried out in the presence of DEA, I- Na+, II- K+, III- NH4+, IV-MEA+, V- DEA+.
Surface-active properties of the synthesized surfactants
Surface-active properties of synthesi-zed sulphat-ederivative salts of highest carboxylic acids ethanol-amides have been studied at the kerosene-water interface at 24 oC using stalagmometric method. The interfacial tension ofdistilled water at the border with kerosene at 22-24 oC was found to be 46-46.5 mN/m and is attributed to the attraction forces between water molecules at the water interface due to the hydrogen bonds. If any foreign molecules are present at the water surface there is a disturbance in the force, leading to a decrease in the interfacial tension.
Aqueous solutions of surfactants con-tain in their composition molecular-dispersed and micelle parts of surfactants, which are in reversible balance. Formation of a new phase in system happens after saturation of the adsorptive layer on an interface at a certain concentration surfactant, so-called critical micelle concentration (CMC). The CMC value is concentration of saturation for everyone separately taken surfactant. It is also necessary to note that the water solubility surfactant is expressed through the CMC parameter. The values of CMC were taken as the concentrations at the point of intersection of the two linear portions of the y-lnC plots. Plots of the surface tension (y) at 24 oC of sulphatederivative salts of highest carboxylic acids ethanolamides vs. the ln of their bulk phase concentration in mol dm-3 (lnC) in water showed that the interfacial tension for
all synthesized surfactants decreases by increasing the concentration of surfactant up to the steady stat that varied according to the type of surfactant.
The obtained products demonstrate high surface activity at the water-kerosene interface and the CMC values are rather close (2.29-3.65) x 103 mol/dm3. It may also be noticed that the values of nCMC (37.08-44.39 mN/m) are relatively higher for surfactants. As is known, spreading pressure for crude oils is in the interval 30-35 mN/m. Therefore, the values of n should exceed 35 mN/m for exhibition of high petroleum-collecting and dispersing capability by surfactants. Also one of the main requirements for surfactants as the collector of oil is a low value of CMC. Namely for these reasons it was of great interest to study petroleum-collecting and petroleum-dispersing properties of surface tants.
Petroleum-collecting and dispersing proper-ties of the synthesized surfactants
Oil collecting and dispersing abilities of reagents synthesized on the basis of cottonseed oil on the crude oils of Pyrallahy, Balakhany and Naphtalane on the surface of the tap water and sea water were investigated. The optimal selection of compositions of petroleum-collecting rea-gents is defined by interrelation a structure surfactant and their colloidal and chemical properties. The paper [19] establishes the main provisions that allow to optimize a choise of surfactants for the development of collectors. The reagents CDIV and CDV have shown high collecting activity of Pyrallahy oil in the both water environment, so that in the sea water environment CDIV - K = 22.2, t = 0-24 hours, CDV - K = 22.2, t = 24 hours; in the tap water environment CD, - K = 25.0, t = 0-48 hours;
IV max. ' '
CD - K = 25.0, t = 24 hours. Also in the sea water
V max.
environment maximum oil collecting activity has been shown CMIV (Kmax = 25.0, t = 24-96 hours), which is dispersing thin layer ofPyrallahy oil in the moment of the introducing reagent (Kd = 95.2%, t = 0 h).
In the sea water environment after 3 days impaction, reagent CMV (Kmax = 44,4, t = 72-96 h) has shown very strong collection activity of Balakhany
oil, which was dispersing in the first introduction moment and next 24 hours duration (Kd = 93,7%, t = 0 h; K = 95.5%, t = 24 h; K = 25.0, t = 48 h; K =
' d ' ' ' ' max.
44.4, t = 72-96 h) and has mixed effect with this. In tap water environment the reagents CDm (Kmax = 25.0, t = 24 h) and CDV (Kmax = 25.0, t = 24h) show maximum collecting ability with Balakhany oil.
The reagent CDV (Kmax = 21.0, t = 24 h) collects the thin layer of Naphtalane oil over the sea water with high coefficient. Same high collecting ability was shown by CDIV (Kmax = 18.0, t = 24 h) and CDV (Kmax = 18.0, t = 0 h) in tap water environment.
The synthesized salts were investigated as anticor-rosive reagents inhibiting hydrogen sulfide corrosion. Anticorrosiveproperties of the synthesized surfactants The study of the protective efficiency of reagents from hydrogen sulfide corrosion of steel grade St3 was carried out by gravimetric method at room temperature using polished samples in a two-phase system kerosene-water (1:9) with stirring during the whole experiment with a magnetic stirrer. Water saturated with hydrogen sulfide was used as the aqueous phase. Hydrogen sulfide
500 mg/1 in the solution was formed by the reaction of the calculated amount of Na2S with an excess of HCl. The duration of the experiment was 5 hours. Intensive mixing of the corrosive environment causes an increase in the corrosion rate in hydrogen sulfide-containing environments by 5 times. The test results are shown in (table 1).
The degree of protection (IE,%) salts were calculated in accordance with the following equation:
IE,%= (CR0 - CRi) x 100/CR where CR is the corrosion rate without an inhibitor and CR is the corrosion rate in the presence of an inhibitor.
It is seen from the date of the (Table 1), hydrogen sulfide corrosion rate is lowered in the presence of all reagents and the effectiveness of protection is increased with increasing concentration of the inhibitor. The inhibitory effect of reagents can be attributed to the adsorption of these molecules on the metal surface. With increasing inhibitor concentration, adsorption and coating of the surface in increased, as a result of which the metal surface is effectively protected from environmental exposure.
Table 1. - Protective effects of synthesized surfactants in H2S containing water-kerosene solution
Surfactants Hydrogen sulfide corrosion
Concentration, ppm Corrosion rate, g/sm2 h Inhibition effect,%
1 2 3 4
Without surfactant 0 3.6
CMI 200 1.6452 54.3
500 0.8568 76.2
CMii 200 1.2852 64.3
500 0.4284 88.1
CMiii 200 0.7848 78.2
500 0.216 94.0
CM IV 100 0.5004 86.1
150 — 100.0
CMv 50 0.2844 92.1
100 — 100.0
CDI 100 2.412 33.0
400 1.008 72.0
100 2.088 42.0
1 2 3 4
CDII 200 1.368 62.0
400 0.756 79.0
CDIII 100 2.16 40.0
300 1.152 68.0
CDIV 100 0.504 86.0
150 0.072 98.0
CDV 50 0.288 92.0
100 0.144 96.0
Conclusion off on the surface of the tap and Caspian Sea waters.
In the present work, some salts of sulphate-de- MEA+ and DEA+ complex salts are able to ensure
rivatives of higher carboxy-lic acids ethanolamides effective steel protection against hydrogen sulfide
synthesized on the basis of cottonseed oil were in- corrosion in water-kerosene solution containing
vestigated. Most of them have high petroleum-col- CH2S=500 mg/1 providing strong protection
lecting and dispersing effects of thin petroleum slicks IE = 86-100% at 50-150 ppm.
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