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UOT 661.725.3.002.68
Salimova N.A., Guseinova M.A.
Azerbaijan State Oil and Industry University, 20 Azadlig ave., Baku, AZ-1010
RATIONAL USE OF CUBIC RESIDUES FROM ISOPROPYL ALCOHOL PRODUCTION
Салимова Н.А, Гусейнова М.А.
Азербайджанская Государственная Нефтяная Академия,
Баку, Азербайджан Азадлыг 20, АЗ-1010
РАЦИОНАЛЬНОГО ИСПОЛЬЗОВАНИЯ КУБОВОГО ОСТАТКА ОТ ПРОИЗВОДСТВА
ИЗОПРОПИЛОГО СПИРТА.
Summary. Analysis one of the wastes of sulphate production of isopropyl alcohol-cube residue of the process of dehydration diisopropyl ether was spent.
Physical-chemical methods. Studing of composition allowed to carry out synthesis with getting of useful product.
Резюме. Проведен анализ одного из отходов сернокислотного производства изопропилового спирта кубового остатка процесса абсолютирования диизопропилового эфира.
При исследовании были использованы физико-химические методы анализа. Изучение состава позволили осуществить синтез с получением полезного продукта.
Keys words: ethyl glycol, catalyst KU-2, diisopropyl ether.
Ключевые слова: этилгликоль, катализатор КУ-2, диизопропиловой эфир.
With the advent of new types of engines, the requirements for quality indicators in terms of resistance to oxidation at high temperatures have increased.
The authors of [1] carried out research on the development of hydrocarbon and non-hydrocarbon synthetic lubricants. The interest in synthetic lubricating oils is due to their unique performance properties. Esters of aliphatic fatty acids, which have a low pour point and are in great demand in the Far North, are widely used in the chemical industry. The lubricity of these esters is maintained over a wide temperature range from 650 to 1200C. Esters are also used in the preparation of combination oils.
Ethers have a number of valuable performance properties, for example, relatively high thermal and antioxidant stability, low pour point, low viscosity, which make these ethers very promising for use in electrical devices in different climatic conditions.
The aim of this work is to obtain esters based on high molecular weight acids contained in the waste of
the process of sulfuric acid production of isopropyl alcohol. The propylene oligomers contained in the waste and remaining in the esterification in the esterification give it low-temperature properties, allowing the use of oils in the Far North.
The creation of low-waste and non-waste technology is a fundamentally new approach to the development of the industry of basic organic and petrochemical synthesis, which means the rational use of natural resources and the protection of the environment. Manufacturing processes must be designed so that, if waste is generated, the latter is transformed into new products.
It is known that in the sulfuric acid production of isopropyl alcohol, waste is generated that does not find any qualified application.
Sulfuric acid [2] production of isopropyl alcohol at the Ethylene Polypropylene plant in Sumgait city is accompanied by the formation of a number of byproducts that are numb for qualified use.
In the literature, the results of studies of the process of obtaining esters by alkoxycarbonylation using monohydric low molecular alcohols are given in some detail.
But on the synthesis of esters, in which polyhydric alcohols are used, there are only patent data, from which it is impossible to identify the basic laws of the reaction, and even more so to recommend the technology for the production of these esters.
In this work, we studied the main regularities of the reaction of alkoxycarbonylation of olefins with monohydric alcohols, in which the conversion of olefin
is completely carried out with a two- or four-fold excess of alcohol.
The specificity of the reaction when using polyhydric alcohols to obtain esters creates the need to use an excess of olefin, which is subsequently recycled in the process.
When studying the effect of the ratio of olefin and alcohol, it was found that the best results in the conversion of alcohol and selectivity to diester are obtained at a ratio of 4; with a further increase in the ratio, no additional effect is observed (Table 1).
Table 1.
Effect of the olefin-alcohol ratio on the alcohol conversion and selectivity for esters (160 ° C, 16 MPa,
Olefin-alcohol ratio (mol) Alcohol conversion,% Selectivity
diester mono ether
2 91,3 80,4 7,1
3 98,2 80,2 5,3
4 98,4 85,6 4,2
5 98,4 86,4 5,1
The work [3] presents the results of a study aimed at increasing the yield of diester at pressures below 10 MPa.
An increase in the catalyst concentration from 1 to 3 wt%, at a pressure of 5 MPa, did not give a significant
change in the conversion of monoester to diester. With an increase in pressure in the process to 9 MPa, the effect of the catalyst concentration on the reaction rate of diester formation is observed (Table 2)
Table 2.
Influence of the olefin-alcohol ratio on the alcohol conversion and selectivity for esters
Pressure MPa Concentration Comet,% wt.. Alcohol conversion,% Selectivity
diester mono ether
5 2 97,2 60 36,5
8 1 97,2 82,1 12,2
9 1 97,6 91,2 6,1
10 1 99,9 98,8 0,16
The study of the effect of temperature on the process of esterification of the fraction 140-2500C of the DIE waste with ethylene glycol was carried out at a ratio of reagents: the 140-2500C fraction of the DIE waste to ethylene glycol equal to 1: 1.4 (mol). The temperature was maintained from 140-1600C. The KU-2 catalyst is taken as 1% of the mass. Water was taken into the Dean-Stark trap. The experiment was carried
out at a temperature of 1470C. After the introduction of the reagents into the three-necked flask and when the temperature reached 1470C, water accumulated in the Dean-Stark trap, and when equilibrium was reached, water stopped collecting and the formation of monoesters stopped. The material balance of this process is shown in Table 3.
Table 3
Material balance of the esterification process of the 140-2500C fraction of
Taken Received
Reagents Quantities Reagents Quantities
g % (mass) g % (mass)
Acid in the fraction 140-2500C 65,0 72,2 Unreacted products 43,5 48,3
Ethylene glycol 25,0 27,8 esterificate 42 46,7
H2O 3,0 3,3
Losses 1,5 1,7
Total: 90,0 100,0 Total: 90,0 100,0
The yield of the esterificate is 53.64% of the mass of the theoretically possible.
The study was carried out with the ratio of the reagents: fractions 140-2500C of the waste DIE to
ethylene glycol equal to 1 ^ 1.4 (mol). The temperature varies from 140-1600C. The KU-2 catalyst is used as 1% of the mass. Water is taken from the Dean-Stark trap. An experiment at a temperature of 1580C is
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described below. When the amount of water reached the esterification process at temperature is summarized 4.5, equilibrium was reached. The material balance of in Table 4.
Table 4
Material balance of the esterification process of the 140-2500C fraction of _the DIE waste with ethylene ^ glycol at 1580C._
Taken Received
Reagents Quantities Reagents Количество
g % (mass) g % (mass)
Acid in the fraction 140-2500C 65,0 72,2 Unreacted products 35.6 39,5
Ethylene glycol 25,0 27,8 esterificate 49,3 54,8
H2O 3,4 3,8
Losses 1,7 1,9
Total: 90,0 100,0 Total: 90,0 100,0
The esterificate yield is 63.2% of the theoretically possible.
The study was carried out at a ratio of reagents: fractions 140-2500C of DIE waste to ethylene glycol 1: 1.4 (mol). The temperature was maintained from 140-
1600C. The KU-2 catalyst is used in the amount of 1% of the mass. Water accumulates in the Dean-Stark trap. An experiment at a temperature of 1660C is described below. The material balance of the process is summarized in Table 5.
Table 5
Material balance of the esterification process of the 140-2500C fraction of
Taken Received
Reagents Quantities Реагенты Quantities
g % (mass) g % (mass)
Acid in the fraction 140-2500C 65,0 72,2 Reagents 12,8 14,2
Ethylene glycol 25,0 27,8 Unreacted products 70 77,8
esterificate 6,0 6,7
H2O 1,2 1,3
Total: 90,0 100,0 Total: 90,0 100,0
The esterificate yield is 93.5% of the theoretically possible.
Physicochemical properties of ethers of fraction 140-250оС of
Table 6
Boiling point temperature limits, °C Refractive index, n|0 Density, g/cm3 Pour point, 0С Flash point in an open crucible, 0С Kinematic viscosity cst.mm3/s at temperatures
200С 500С
110/2 - 120/2 1,4620 851,3 -82 н.з 72 - 4,16
185/2 - 200/2 1,4902 881,6 -75 138 21,4 9,8
CONCLUSIONS
1. As a result of the esterification reaction of the 140-2500C fraction of diisopropyl ether waste, which was obtained as a result of sulfuric acid production of isopropyl alcohol with ethylene glycol, an esterificate was obtained that meets all the requirements for transformer oils.
2. It was revealed that the reaction of formation of ethylene glycol ethers with unsaturated aliphatic acids proceeds in 2 stages. The reaction products contain both monoesters and diesters
3. The distinctive property of the synthesized product - low pour point has been established. This allows us to recommend it for use in the Far North.
REFERENCES
1. F. M. Shakhverdieva, N. A. Salimova, M. A. Guseinova "Expanding the resources of the synthesis of a dielectric fluid" // Oil refining and petrochemistry No. 5-2014, p. 37
2. Salimova N.A., Shakhverdieva F.M., Guseinova M.A. - Synthesis of a dielectric fluid based on the waste of sulfuric acid production of isopropyl alcohol // - Oil refining and petrochemistry № 11-2012, p 42
3. Salimova N.A., Shakhverdiyeva F.M., Amirov S.G., "Waste recycling" Baku-2011, art.99.
4. Synthesis of anionic detergents based on wastes of sulfuric acid hydration of propylene. Processes of petrochemistry and oil refining, 13.1 (49), Baku, 2012, pp. 20-24
5. Expansion of resources for the synthesis of dielectric fluid. Magazine No. 5. "Oil refining and petrochemistry". Moscow, 2014, p. 37-40. F. M. Shakhverdiyeva N. A. Salimova,
6. Purification and use of the bottom residue obtained in the process of isopropyl alcohol absolutization. Magazine No. 9. "Azerbaijan oil industry". Baku, 2014, p. 43-47 N. A. Salimova, F. M. Shakhverdiyeva E. D. Sadigov
