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DOI: http://dx.doi.org/10.20534/AJT-16-11.12-71-75
Qurbanov Zufar, assistant,
Tashkent chemical-technological institute Ikromov Abduvaxob, professor,
Tashkent chemical-technological institute E-mail: Ulug85bek77@mail.ru
Synthesis of fatty Acid amide by the sherbule reaction based distilled Fatty Acids
Abstract: Field of application of fatty acid amides because of their reactivity is various. Nitrites, primary amines, valuable flotation agents, additives for fuels based on fatty acid amides have been produced. The amides are obtained based on fatty acids. A fatty acid synthesized by oxidation of paraffins. Until recently, the raw material for the production of paraffin's are hydrocarbon sources, such as oil and natural gas, gas condensate, coal and others. It should be noted that, the content of higher hydrocarbons is low in these sources. Various oxidants are used to produce acids from them. The process is conducted under severe conditions at high temperatures and under high pressure. However, because of decreasing fossil fuel and oil reserves, other raw materials for the production of carboxylic acids have to be investigated from scientists. In this regard, distilled fatty acid (DFA) obtained from soapstock is perspective and the separation of individual components is considered as an actual task.
Keywords: amine, amide, sylvinite, fatty acids, chloride, acid.
The world population is growing rapidly, and the They are used in pharmacy, cosmetics, organic syn-fact that is expected to reach more than 9 billion by thesis and in the production of potassium chloride as 2050, it became evident that the world needs to pro- flotation reagent.
duce more food to keep up with the growing number The demand for amines in the "Dehkanabad potash
of mouths to feed. However, increasing number of plant" is 250 tons annually. Amines are not produced in people means further urbanization and therefore less Uzbekistan. Therefore, at the present time they buy farmland to work with, which means that farmers need from foreign countriesfor 3000 USD per ton. With-to increase productivity. It means, by increasing popu- the expansion of capacity of the plant the demands for lation, the demands for the production of potassium amines also increased.
fertilizer also increases. 200,000 tons of export-orient- Higheracid (intermediates of oil and fat industry),
ed import substitution potash annually produced in fuel alcohols (waste products of biochemical plants), Dehkanabad potash plant [1]. Potash fertilizer is pre- as well as urea and sodium hypochlorite can be used as pared from sylvinite. Uzbekistan occupies one of the raw materials for the synthesis of amines [2]. leading place in the world by sylvinite stocks. In the The synthesis of amines is carried out in three stag-
stock of Tyubegatana the sylvinite reserve is 215 mil- es. In a first step the fatty acid amides are synthesized lion tons. Separation of sylvinitefrom ore is carried out according to the following reaction: by flotation and amines can be used in this purpose. R - COOH + CO (NH2)2 = R - CONH2 + NH3 + CO2
Reactions carried out at temperatures about 170180 °C and at atmospheric pressure. In the second stage, primary amines are obtained by Hofmann rearrangement. The process proceeds according to the next reaction: R - CONH + NaClO + NaOH+ CH OH,
2 5
(solute)
=R - NH2 + NaCl + CO2
The second stage reaction is carried out at a temperature near 80 °C and at atmospheric pressure. In the third step, primary amines in the presence of fusel alcohols areconverted to secondary amines:
R - NH2 + R' - OH + K = R - NH - R' + H2O + K In this paper, we havestudied the separation of higher fatty acids and obtaining amides on their basis.
Samples of fatty acids were analyzed by chromatography. At first, fatty acid mixture was treated with diazomethane and transferred their methyl esters. The synthesized fatty acid methyl esters was purified by thin layer chromatography using silica gel adsorbent in the solvent system of hexane/diethyl ether at the ratio of 4:1. The resulting layer of silica gel with methyl ester of fatty acids was treated with iodine vapor. Chloroform was desorbed from silica gel containing methyl ester. After the release of methyl esters from chloroform, samples were placed in a tube and through the adsorbent passed over the solvent hexane [3].
Then, the analysis were carried out on the instrument Agilent Technologies 6890 N equipped with a flame ionization detector at a temperature of between 50 °C - 270 °C, in a capillary of 30 m length, filled with the nonpolar phase HP-5. Carrier gas was helium with-the rate of 30 ml/min.
Studied fatty acid composition is shown in Table 1. It can be observed from the table that in the investigated samples of fatty acids mainly contains palmitic (C15 H31 C00H-30,3%), oleic (C17 H33 COOH - 22,7%) and linoleic (C17 H31 COOH- 421,396) acids. The study determined on samples of Kattakurgan oil and fat manufacture containing 10 different fatty acids. Exactly, 7 ofsaturatedfattyacids (total - 34.4%) C9 H19 COOH, COOH, C15 H31 COOH, C16 H„ COOH,
C13 H27
31
33
C17 H35 COOH, C19 H39 COOH and 3 unsaturatedfatty-acids (total - 65.7%) C16 H31 COOH, C17 H33 COOH and
Ci7 H3i COOH
To separation of certain components of fatty acids, distillation temperature were analyzed. Reference data showed that the distillation temperature of palmitic, oleic and linoleic acids are 230.7 °C, 232.0 °C and 230233 °C at a pressure of 15 mmHg, respectively.
These data show that the temperature in the vacuum distillation of all three fatty acids have substantially
similar values. Therefore, the separation into the individual components by a process of distillation ofa mixture of fatty acids from DFAin the laboratory revered impractical. The melting point of the fatty acids are very differen: palmitic acid - 62.5-64.0 °C; oleic acid - 13.4-16.8 °C and linoleic acid 5-5.2 °C. This enabled us to separate a technical fatty acid to separated components with small amounts of other fatty acid impurities [4].
Table 1. - The composition of fatty acids,%
Fatty acids t %
Caproic acid10:0 0.1
Myristic acid 14:0 1.0
Palmitic acid 16:0 30.3
Palmitoleic acid 16:1 0.7
Margarine acid 17:0 0.1
Stearic acid 18:0 2.5
Oleic acid 18:1 22.7
Linoleic acid 18:2 42.3
Arachidic acid 20:0 0.2
Behenicacid 22:0 0.1
Thus, samples of fatty acidsfrom Kattakurgan fat-and-oilmanufacture, are studied. The composition of the fatty acids are determined on the instrument Agilent Technologies 6890 N. Individual components, such as palmitic acid, oleicacid and linoleic acid are separated from the mixture offatty acidsbased on melting points, in the technical form including small amount of other fatty acids.
Table 2. - Composition of fusel oil
Composition %
Isoamylalcohol 65-75
Isobutylalcohol 4-8
Propylalcohol 5-7
Ethanol 1-2
Aldehydes 0,01-0,05
Octyl-nonylalcohols 0,1-0,2
Furfural 0,01-0,02
Fattyacids 0,01-0,05
Water 10-15
Other components ~ 1
Data in the table are averaged accordingly data taken from four different manufactures.
The purpose of research is to provide secondary and tertiary fatty amines. At the first stage we received amides of the DFA on Sherbule reaction.At the second stage, the primary fatty amines are produced by Hoffman rearrangement reaction.At thethird stage, secondary and
tertiary fatty amines by alcoholysis of primary amines with alcohols of fusel oil (wastes of biochemical plants) [5]. In this purpose, the chemical composition of fusel oilssampled from biochemicalmanufactures of Uzbekistan (Yangiyul biochemical plant, Bektemir alcohol plant, Kokand alcohol plant and Andijan biochemical plant) have been studied.
Fusel oil is an oily liquid with a strong unpleasant odor, from light yellow to reddish-brown color with a density of0.82-0.85 g/cm 3 (at 20 ° C). The composition and properties vary depending on the raw material and
the fermentation conditions and selection of fractions at distillation process. The distillation yield of crude alcohol - 0.4-0.8%.
The main components of fusel oil are monohydric saturated alcohols of C3-C9, which the main component is isoamyl alcohol. In addition, isobutyl alcohol, propyl alcohol and small amounts of higher alcohols and aliphatic aldehydes, fatty acids, and furfural also can be found from the composition (Table 2).
Fusel oil is fractionated on a continuous pilot plant (Figure 1).
Fractionation of substances is conducted depending on boiling points of components containing in the fusel oil. The reflux ratio in the columns is determined by the allocation of the next light volatile fractions. Each separated fraction is fractionated once again in the pilot plant.
Aliphatic amides of cottonseed oil fatty acids synthesized by Sherbule method through the interaction of urea with fatty acids:
R - COOH + CO(NH2)2 = R - CONH2 + CO2| + NH3|;
R = C12-22H25-45
The synthesized amides were characterized by IR spectrometer "Agilent Technology FTIR-640" (USA) (Figure 2) and gas chromatography-mass spectrometry with gas chromatography complex "Agilent" (Figure 3).
The vibrational transitions for synthesized amides were identified based on the recorded FT-IR spectra in the range of 4000-400 cm-1; the total number of scans is 12.
Figure 3. Chromatography/Mass Spectrometry mixtures of aliphatic fatty acid amides
Figure 2. IR spectra of the synthesized fatty acid amides
Chromatography/mass spectrometry investigation of the mixture was carried out on a gas-chromatography complex "Agilent 6890B" with mass selective detector "Agilent 5973 inert"; ionization energy of 70 eV; ion source temperature of 230 °C; the temperature of mass filter of 180 °C. Separation was performed on a capillary column HP-5ms, 30m x 0.32mm, stationary phase thickness of 0.5 0^m (Agilent, USA). Helium was used as carrier gas; carrier gas flow — 1.1 ml/min, input mode — Split 1:20. Separation was carried out in the temperature programming mode: isotherm 170 °C for 4 min, heated to 280 °C at 5 °C/min, isotherm 280 °C for 15 min. Evaporator temperature — 280 °C, sample injection volume of 4^l. Detector interface temperature of 300 °C. Sample preparation. 0.02 g of a mixture of fatty acid amide is dissolved in 5 cm 3isoamyl silsV sj'eV s'i.'oV Vi'f; 'tWs alcohol (Figure 3).
Studied acid amides can be used as intermediate products for the synthesis of amines by Hoffmann
Application of mud composition at the opening of unstable clay deposits
rearrangement. The secondary and tertiary amines widely from oil industry wastes. IR spectrometry and gas used as a flotation agent.Thus, aliphatic amides were chromatography/mass spectrometry were conducted in synthesized based on the fatty acid mixtures obtained order to analysis of a mixture ofaliphatic fatty acid amides.
References:
1. Osichkina R. G., The raw material base of potash and halurgical industry in Uzbekistan, Uzbek chemistry journal, - 2001, - V2.
2. Gitis S. S., Glaz A. N., Ivanov A. V. Workshop on Organic Chemistry of Organic Synthesis, - Moscow, - 1991, - P 303.
3. Weigand K., Experimental methods in organic chemistry, - Moscow. - 1952, - P737.
4. Reutov O. A., Kurs A. L., Butin K. P. Hofman rearrangement.Organic chemistry, Part 4. - Moscow. - 2004. - P. 367-368.
5. Yettiboeva L. A., Gapparov C., Kadirov O.Sh. The chromatographic analysis of fatty acids in the composition of waste of Gulistan fat-and-oil plant, Actual problems of analytical chemistry, IV Republican scientific conference, - 2014, - Volume 1, - P. 303-305.
DOI: http://dx.doi.org/10.20534/AJT-16-11.12-75-77
Mahamathozhaev Dilmurad Rahmatovich, Tashkent State Technical University, senior research fellow researcher of the department «Drilling oil and gas wells E-mail: sunnatilla29@rambler.ru
Application of mud composition at the opening of unstable clay deposits
Abstract: This paper presents the results of laboratory studies on the development of the composition of inhibiting clay-free drilling fluid and the results of its industrial tests in drilled wells AK "Uzgeoburneftegaz". Keywords: montmorillonite, scree, landslide, taking the drilling tool, the oil bath that inhibits mud.
In the oil and gas fields in Uzbekistan there are powerful clay deposits consisting of montmorillonite, siltstone, mudstone, and others. Argillaceous rocks. Autopsies clay deposits is often accompanied by talus and landslides wells wall, caused by the interaction of the filtrate used clay mud with passable argillaceous rocks [1, 236-239].
For example, in the area occurred Darahtli № 2 sticking drilling tool due to violation ofthe integrity ofthe well bore. To eliminate the sticking of the drilling tool it took 2757 hours. That's the reason stated above in the squares Kokdumalak № 412, 428, Taylok № 9, № 20 North Shur-tan, Qamar № 1, Girsan № 29, № 35 and other Chul-kuvar occurred sticking drilling tool for the elimination of which spent a huge calendar time and material and technical resources [2, 168-170].
Due to the fact that the cut oil and gas wells, consists of different types of rocks and composition, will act not identical under identical conditions, the mud filtrate. Therefore, the most important factor in maintaining the stability of the borehole is the right choice of the type of
drilling mud and its composition, as well as technological parameters [3, 192-198].
The standard formulation of drilling fluids is regulated to maintain filtration indicator while drilling argillaceous rocks less than 10 cm3/30 minutes, which should be provided work reagents stub analyzer in an alkaline medium, ie. E. At a pH greater than 7, especially at elevated temperatures and salinity. But argillaceous rocks have minimum filtration capacity relative to the liquid hydrocarbon — oil (oil fields tires) and water based systems — muds.
At pH = 7 the concentration of hydronium ion (H30 +) and hydroxyl (OH-) is the same. In the case of drilling fluids with pH> 7 the equilibrium dissociation constant is displaced to the right, ie. E. The amount of hydroxyl ions dissociated increases. In this case, the diffusive mass transport begins concentration equalization between mud filtrate and Doi clay-pore, resulting in cell structure from compensation, in general, to weaken bonds between layers and, ultimately, to shattering rock at the borehole wall.
