CC BY
63
Section 1. Technical sciences
https://doi.org/10.29013/AJT-20-3.4-3-9
Rakhimov Dilshod Pulatovich, Tashkent chemical-technological institute, Uzbekistan
E-mail: [email protected] Abdullaev Utkir Saidakbar ugli, Tashkent chemical-technological institute, Uzbekistan E-mail: [email protected] Rakhimov Pulat Hadjievich, Urganch State University, Uzbekistan E-mail: [email protected] Ruzibaev Akbarali Tursunbaevich, Tashkent chemical-technological institute, Uzbekistan
E-mail: [email protected]
GETTING A MODIFIED INTERESTERIFICATION USING THE COMBINATION OF LIQUID OILS AND SOLID FAT
Abstract. The aim of this work is to develop modified transesterifications with a reduced trans-acid content as local raw materials using liquid vegetable sunflower oils and solid fats with hydrogenated cotton oil using the method of chemical transesterification.The reason is not the use of our internal raw materials, which have a lot of transisomers in the composition of hydrogenated cotton oil. In recent years, worldwide attention has been focused on the problem of transisomers of fatty acids in foods. The production of transesterified fats is a fundamentally new stage in the development of the fat processing industry, which provides a significant improvement in the quality of finished products. From the beginning, we compiled the reaction for the samples according to the corresponding ratio to № 1-ini-tial sunflower oil, № 2 - hydrogenated cotton oil and transesterification formulations: № 3-60/40, № 4-75/25, № 5-80/20, № 6-90/10. The possibility of lowering trans acids in solid fats with the process of modifying oils and solid fats based on sodium methylate catalyst was established.
Keywords: hydrogenated cottonseed oil, trans acid, esterification, methylate sodium catalyst.
Introduction. The development of the economy raw materials necessary for human life are produced for
of the Republic of Uzbekistan, the provision of indus- industrial sectors. They are of particular importance
try with raw materials, and the population with food for the primary or integrated processing of farmer
products. The two main areas of agriculture are farm- and livestock resources and the material support of
ing and animal husbandry; the primary foodstuffs and the people. Therefore, great attention was paid to the
processing of agricultural products in the first stage of economic reforms in Uzbekistan thanks to the President Shavkat Mirziyoyev Miromonovich [1]. The food industry is the main sector of the economy, socially protecting and supporting the population, providing with additional jobs, and also forming the budgets of small and large regions. The food industry includes many enterprises producing meat and dairy, fish, flour, bakery and confectionery, pasta, canned fruits and vegetables, tea, winemaking products and champagne, alcohol, tobacco products, beer and soft drinks, soap and especially oil and fat. The task ofcontinuously providing the country's population with high-quality food products determines the need for the development of the food industry and as an oil and fat industry. The oil and fat industry of our Republic has rich experience and potential that allows it to occupy a leading place in the national economy. This industry is mainly focused on the processing of local raw materials [2]. Nowadays, the spread and margarine industry are very developed, but for them the raw materials are modified fats, transesterifications come from abroad [3]. The reason is not the use of our internal raw materials, which have a lot of transisomers in the composition of hydrogen oil. In recent years, worldwide attention has been focused on the problem of transisomers of fatty acids contained in food [4]. They are found in nature and are formed during hydrogenation [5]. For example, in milk and fat of ruminants, their amount does not exceed 5%, and in the process of hydrogenation it can reach 50%. Many scientists who have conducted research in this area believe that uncontrolled interference in the nature offats can cause serious harm to human health. In many countries, the limit of such interference is defined and restrictions on the content of trans isomers in food products have been adopted at the legislative level. At present, there are two modi-
fication methods that allow one to obtain specialized fats without transisomers of fatty acids or with a low content ofthem: transesterification - depending on the type of catalyst, chemical and enzymatic (enzymatic) [6]. Transesterification of oils and fats is widely used in the UK, Germany, Holland, Japan, Belgium, Canada, the USA and other countries to effectively solve many problems in the production of spreads, margarines, fats for the confectionery and baking industries, including for: creating products, not containing transisomers of fatty acids; creating an optimal range of products for various purposes in terms of acid composition and rheological properties with a limited selection of raw materials [7]. The production of transesterified fats is a fundamentally new stage in the development of the fat processing industry, which provides a significant improvement in the quality of finished products [8]. The transesterification of fats and oils consists in the intra- and intermolecular redistribution offatty acids in a mixture of triglycerides [9]. In the production of edible fats, mainly chemical intermolecular and intramolecular transesterification is used, which consists in the redistribution offatty acid radicals under the influence ofhomogeneous catalysts [10]. Currently, transesterification is carried out mainly with sodium methylate or ethylate [11]. The aim of this work is to develop modified transesterifications with a reduced trans-acid content as local raw materials using liquid vegetable sunflower oils and solid fats with cotton hydrogenated oil using the method of chemical transesterification.
Objects and research method. To transesterify, we needed liquid sunflower oil with the color 5 red unit, acid number 0.2 mg KOH; brand -5 cotton hydrogenated oil, melting point 43 °C, acid number 0.4 mg KOH, hardness 360 g/cm. As a catalyst, we used sodium methylate, the indices of which are given in (Table 1).
Table 1.- The technological characteristics of the catalyst
Catalyst Range of working concentrations,% Operating temperature range, °C Reaction time, min
sodium methylate 0.1-0.15 50-120 5-120
To conduct the reaction, we from the beginning compiled a sample for the samples according to the corresponding ratio to № 1 - initial sunflower oil, № 2 - hydrogenated cotton oil and transesteri-
Table 2.- The character
fication formulations: № 3-60/40, № 4-75/25, № 5-80/20, No. 6-90/10. The fatty acid composition of the oil and the original hydrogenated cotton oil are given in (table 2). cs of the initial samples
Name of initial samples Fatt ty Acid Composition Acid number number of saponification Refractive Index, 25 °C Mp °C
14:0 16:0 16:1 17:0 18:0 18:1 18:2 20:0 20:1 22:0 24:0
Sunflower oil 0.08 6.84 0.09 - 3.84 27.45 58.14 0.26 0.14 0.77 0.23 0.2 192 1.473 -19
Hydrogenated cotton oil 0.72 22.75 0.20 0.22 17.60 9.78 1.89 0.29 0.26 0.14 - 0.4 197 1.471 43
The transesterification process appears to be proceeding under vacuum, but for laboratory conditions, we were used under a pressure of 1 atm of nitrogen as an inert gas and to interrupt the reaction of a 25% NaCl solution [12]. For this experiment, glassware was collected; a chemical glass with a capacity of 500 cm3; magnetic stirrer; dividing funnel per 1000 cm3, an autoclave with a capacity of 1 l was installed, which is equipped with a nichrome spiral and nozzles for nitrogen supply, with a manometer [13]. 400 g of the mixture was weighed into a glass with an accuracy of 0.01 g, consisting of solid and liquid fats, its melting point was determined and heated to dry at a temperature of 120 °C for 0.5 h with vigorous stirring. Magnetic stirrer speed 2.0 s-1. Then, the contents of the autoclave were cooled to a transesterification temperature of 90 °C [14]. Without stopping stirring, the catalyst was added in an amount of1% to the autoclave, in the form of a 10% oil suspension, and closing the lid, nitrogen was supplied up to 1 atm pressure, stirring was continued for a predetermined time at the same temperature [15]. The reaction mixture was placed in a separa-tory funnel and washed with 300 cm3 of hot 95 °C 25% NaCl solution to destroy the catalyst, and then with hot water until neutral by methyl orange [16]. The transesterified fat was filtered through a paper
filter and the melting point and hardness were determined, which is shown as a result of the discussion in (Table 4). The acid number was determined for the initial samples and the obtained transesterifications with the method for determining the acid number of light oils. This method is based on titration of a fat sample with an alkali metal hydroxide solution in the presence of a phenolphthalein indicator [17]. As a solvent for fat, a neutralized mixture of alcohol with diethyl ether or gasoline is used. Reagents: a neutralized mixture of 96% ethyl alcohol and diethyl ether (1: 2), 1% alcohol solution of phenolphthalein; Chemical glassware: flat-bottomed wide-necked flask with a capacity of 100 cm3. Technique of execution. 3-5 g of fat was weighed into a flask on an analytical balance, 50 cm3 of a neutralized mixture of diethyl ether and ethyl alcohol were poured, and the fat was dissolved. 3-5 drops of a 1% phenolphthalein solution were added to this. The resulting solution with constant stirring was titrated from the burette with a 0.1 m alcohol solution of alkali metal hydroxide until a faint pink color appeared that did not disappear for 30 s [18]. The results of acid numbers are given in (tables 2, 4).
For chromatographic data on the original sunflower oil and hydrogenated cotton oil are shown in (figures 1, 2).
Figure 1. Chromatogram of the fatty acid composition of the original sunflower oil
Figure 2. Chromatogram of the fatty acid composition of the starting cotton hydrogenated cotton oil
Results and discussion. Results are presented in (table 3). The obtained data on transesterification experiments are given [19]. To determine the composition of fatty acids, the presented samples, which are shown in the pictures of chromotograms 1.2 and transesterification images: No. 1-60/40, No. 2-75/25, No. 3-80/20, No. 4-90/10 were hydro-lyzed with 10% methanol KOH solution in the ratio of sample: solution 1:10, while boiling in a water bath for 1 hour [20]. The resulting soaps were decomposed
Table 3.- Fatty acid composition of
with a 50% aqueous solution of H2SO4. Fatty acids were extracted three times with diethyl ether. Next, the ether extracts were washed with distilled water to a neutral medium, dried over sodium sulfate, and then the ether was distilled off. Fatty acids were methylated with freshly prepared diazomethane. The obtained methyl esters were purified in a thin layer of silica gel in a hexane: diethyl ether 4: 1 solvent system, the ME zone was shown in J2 vapors, and methyl esters were stripped with silica gel with chloroform.
the studied samples,% GC by weight
Fatty acid Source oil Samples Hydrogenated cotton fat
№ 1 № 2 № 3 № 4
1 2 3 4 5 6 7
Myristine 14:0 0.08 0.48 0.58 0.61 0.68 0.72
Palmitic 16:0 6.84 16.82 19.30 19.85 21.57 22.75
Palmitoleic 16:1 0.09 0.14 - 0.18 0.25 0.20
1 2 3 4 5 6 7
Margarine 17:0 - 0.16 - 0.20 0.20 0.22
Stearin 18:0 3.84 12.49 14.58 15.05 16.28 17.60
Oleic 18:1 27.45 16.47 13.95 13.38 11.38 9.78
Linoleic 18:2 58.14 22.79 14.68 12.56 6.78 1.89
Peanut 20:0 0.26 0.29 0.27 0.30 0.28 0.29
Eicosene 20:1 0.14 0.19 - 0.27 0.24 0.26
Begenova 22:0 0.77 0.40 0.29 0.28 0.19 0.14
Lignoceric 24:0 0.23 0.17 - 0.12 0.09 -
After chloroform removal, the MEs were dissolved in hexane and analyzed on an Agilent Technologies 6890 N instrument with a flame ionization detector using a 30 m long capillary column with an inner diameter of 0.32 mm with an deposited HP-5 phase at temperatures from 150 to 270 °C. The carrier gas is helium.The composition and content of fatty acids are presented in (table 3).
From (table 3). It can be seen that, horizontally from left to right, an increase in the concentration of solid fats increases the mass fraction of saturated fatty
acids and unsaturated decreases. After washing and drying, the samples do not appear stratification of oils and fats. This is due to the intermolecular and intramolecular interchangeability of acyls (transesterifica-tion) in triglycerides in the presence of an alcoholate catalyst. Transesterification is used in industry to reduce the content ofhigh-melting glycerides and trans isomers in fats. In (table 4) shown by lowering the transisomers from the initial hydrogenated cotton oil sequentially to recipe № 1 and as a result, the melting point of the transesterifications decreass.
Table 4.
Samples The content of trans isomers % Saturated Fatty Acid % Unsaturated fatty acid % Melting point °C Hardness. g/cm A.n. mg КОН
No. 1 29.60 30.81 69.19 28 80 0.2
No. 2 36.35 35.02 64.98 34 120 0.3
No. 3 37.20 36.41 63.59 36 320 0.2
No. 4 42.06 39.29 60.71 39 360 0.3
Hydrogenated cotton oil 46.37 41.5 58.5 43 500 0.4
Similar fats are obtained by transesterification of mixtures containing hydrogenated fats. Transesteri-fied fats containing 25-35% saturated and 30-35% transmonosaturated fatty acids have a melting point of 32-33 °C, a hardness of 90-120 g / cm and are used either as ready-made greasy bases of squared margarines and cooking fats, or as their plasticiz-ing component. Today, the margarine industry in Uzbekistan is developing on a large scale, mainly the methods of emulsion crystallization on rollers
are well developed. We believe that the conclusions drawn from this experiment can be effectively applied in our similar certified products, which are produced as raw materials for margarine.
Conclusions. The possibility of lowering trans acids in solid fats with the process of modifying oils and solid fats based on sodium methylate catalyst was established. The most active transesterification catalysts include sodium methylate and ethylate. These catalysts even at relatively low temperatures
(0-130 °C) interact with mono-, di-, and triglycer- even small quantities of which the transesterification
ides to form sodium glycerates, in the presence of reaction is sharply accelerated.
References:
1. Ukaz Prezidenta Respubliki Uzbekistan ot 07.02.2017 g. N UP-4947 "O Strategii dejstvij po dal'nejshemu razvitiju Respubliki Uzbekistan". Decree of the President of the Republic of Uzbekistan dated 07.02.2017 N UP-4947 "On the Strategy for the Further Development of the Republic of zbekistan".
2. Eychenne V., Debrauwer L., Mouloungui Z. O-etherification between glycerol and glycerol monooleate -Demonstration of formation of diglycerol monooleate and triglycerol monooleate by fast atom bombardment-mass spectroscopy and 13C nuclear magnetic resonance. Journal of Surfactants and Detergents, 2000.- Vol. 2.- No. 3.- P. 173-177. Doi:10.1007/S11743-000-0122-3.
3. Rahimov D. P., Salijanova SH. D., Ruzibaev A. T., Achilova S. S., Sanaev E. SH. Determination of the optimal temperature regime during cooling and crystallization in the production of margarine for a layered pastry. Universum: himiya i biologiya, 2019.- Vol. 66.- No. 12.- P. 95-100.
4. Ivashina O. A., Tereshchuk L. V., Starovojtova K. V., Tarlyun M. A. Interesterification as an alternative way to modify transisomer free fats. Tekhnika i tekhnologiya pishchevyh proizvodstv. 2015.- T. 38.-No. 3.- P. 18-23.
5. Ruzibayev A. T., Kadirov Y. K., Rahimov D. P. Intensification ofthe hydrogenation process ofvegetable oils with effective methods of detoxication of catalyst. European Applied Sciences, 2015.- No. 5.- P. 58-61.
6. Raquel C. R., Veronique G., Roland V., Wim D. G. Chemical and Enzymatic Interesterification of a Blend of Palm Stearin: Soybean Oil for Low trans- Margarine Formulation. Journal of the American Oil Chemists' Society. 2009.- Vol. 86.- Issue 7.- P. 681-697.
7. Tereshchuk L. V., Mamontov A. S., Starovojtova K. V. Palm Oil Fractionation Products in Spread Production. Tekhnika i tekhnologiya pishchevyh proizvodstv. 2014.- No. 3.- P. 79-83.
8. Frank D. Gunstone, vegetable oils in food technology (Composition, Properties and Uses).- USA published 2002.- 337 p.
9. Oku T. Nonoguchi M. Moriguchi T. Method of production of fatty acid alkyl esters and / or glycerine and fatty acid alkyl ester-containing composition. Patent World Organization, 2005; 021697, 2005.
10. Koritala S. Selective hydrogenation of soybean oil. III. Copper-exchanged molecular sieves and other supported catalysts. Journal of the American Oil Chemists Society, 1968; 45(3), 197-200. DOI: 10.1007/ BF02915351.
11. de Luna M. D. G., Cuasay J. L., Tolosa N. C., Chung T. W. Transesterification of soybean oil using a novel heterogeneous base catalyst: synthesis and characterization of Na-pumice catalyst, optimization oftransesteri-fication conditions, studies on reaction kinetics and catalyst reusability. Fuel. 2017.- V. 209.- P. 246-253.
12. Arutyunyan N. S., Yanova L. I., Arisheva E. A., Kosachev V. S., Kamyshyan M. A. Laboratory Workshop on Fat Processing Technology. - Moscow, Agropromizdat, 1991.- 160 p.
13. Eychenne V., Debrauwer L., Mouloungui Z. O-etherification between glycerol and glycerol monooleate -Demonstration of formation of diglycerol monooleate and triglycerol monooleate by fast atom bombardment-mass spectroscopy and 13C nuclear magnetic resonance. Journal of Surfactants and Detergents, 2000.- Vol. 2.- No. 3.- P. 173-177. Doi:10.1007/S11743-000-0122-3.
14. Issariyakul T., Dalai A. K. Comparative kinetics of transesterification for biodiesel production from palm oil and mustard oil. Can. J. Chem. Eng. 2012.- V. 90.- P. 342-350.
15. Ma Y., Wang Q Sun X., Wu C., Gao Z. Kinetics studies of biodiesel production from waste cooking oil using FeCl3-modified resin as heterogeneous catalyst. Renew. Energy. 2017.- V. 107.- P. 522-530.
16. Xingguo Wang., Wei Wei._Triacylglycerols fingerprint of edible vegetable oils by ultra-performance liquid chromatography-Q-ToF-MS. 18 Jun, 2019. Version 1. DOI: 10.17632/hdxtr557jc.1
17. Maynard Joslyn. Methods in Food Analysis. eBook ISBN: 9780323146814, Academic Press, 1st January 1950.- 534 p.
18. Rashid U., Anwar F. Production ofbiodiesel through optimized alkaline- catalyzed transesterification of rapeseed oil. Fuel. 2008.- V. 87.- P. 265-273.
19. Christopher Pohl., Nebojsa Avdalovic., Kannan Srinivasan., Satinder Ahuja.Ion Chromatography.- V. 13. Instrumentation, Techniques and Applications, 1st Edition, 9780128130766, Academic Press, 1st October, 2020.- 400 p.
20. Rakhimov D. P., Ruzibaev A. T., Tashmuratov A. N., Salijanova Sh. A. Research of the process of obtaining interesterified fat for margarine production on the basis of sunflower oil and palm stearin. Food science: Chemistry and chemistry technology journal, 2020.- Vol. 1.- No. 1.- P. 64-68.
