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ISSN 2522-1841 (Online) AZERBAIJAN CHEMICAL JOURNAL № 3 2023 105
ISSN 0005-2531 (Print) UDC 665.753.4
OBTAINING OF ECOLOGICALLY CLEAN DIESEL FUEL BY EXTRACTION PROCESS UNDER THE INFLUENCE OF MAGNETIC FIELD
B.G.Abdulov, A.A.Hasanov
Azerbaijan State Oil and Industrial University
Received 13.12.2022 Accepted 01.02.2023
Currently, polycyclic aromatic hydrocarbons in the diesel fraction obtained by direct oil refining do not meet the standards. This problem is solved in different ways. The extraction process was used as a more efficient method in this study. The aim is to purify polycyclic aromatic hydrocarbons from the diesel fraction obtained during the primary processing of crude oil, using the extraction method under the influence of a magnetic field. Studies have shown that it is advisable to use high-purity N-methylpyrrolidone as extractant for the extraction of polycyclic aromatic hydrocarbons from the diesel fraction. In addition, depending on the degree of acidity, 3 different acids were used - acetic, phosphate and sulfate. The optimal process conditions are as follows: ratio 1:1:1 (N-methylpyrrolidone: Acid: Diesel), magnetic field intensity - 20 mT, speed of stirrer - 70 cycles/minute. While using solely N-methylpyrrolidone as an extractant under magnetic field with an intensity of 20 mT, diesel fuel was obtained with a content of 6 % (wt.) aromatic hydrocarbons, which corresponds to the EURO-5 standard.
Keywords: diesel, extraction method, magnetic field, N-methylpyrrolidone.
doi.org/10.32737/0005-2531-2023-3-105-m
Introduction
Transportation emission are a key talking point when it comes to environmental pollution. The ever-increase demand to move people and goods further, faster and the growth in freight vehicles are one of the many contributors to overall pollution. Consequently, increasing in adverse human health effects and climate changes as led government and legislative bodies across the world to clamped down on standard updates for emissions. In the European Union (EU), continuous improvement in fuel quality has led to stricter requirements for flue gases emitted during engine combustion. EU demand for fuel has led to the supply of sulfur-free fuel to European regions. EN-590 reflects the demand for diesel fuel for sale in the European Union [1].
Current and future environmental requirements for diesel fuels limit the content of arenas and sulfur in them. Traditional technologies for hydrotreating diesel fractions ensure the achievement of the required performance, special processes of catalytic hyd-
rodearomatization at high pressures and require the use of expensive catalysts.
However, there is another point of view [2], according to which the processes of hyd-roprocessing have practically reached the limit of their efficiency and increase the sulfur content in oil products to 0.005 % wt. and lower using this method is possible, but it is not economically viable. In this regard, the search for new, unconventional methods for removing sulfur from motor fuels is of particular relevance.
Extractive dearomatization processes take place at relatively low temperatures and pressures, and along with raffinate, a component of diesel fuel with a low arene content, they make it possible to obtain an extract -arene concentrate, which can be used as a petrochemical feedstock.
Diesel fractions consist of a mixture of hydrocarbons of various classes and hetero-cyclic compounds of various structures. The physical properties of hydrocarbons depend both on their belonging to a certain class and on their molecular weight. The physical properties
of heterocyclic compounds differ from those of hydrocarbons. In particular, all these compounds dissolve in different ways and at different temperatures (selectively) in a number of organic solvents [3, 4].
Selective solvents are those liquids that have the ability to extract only some specific components at certain temperature from a mixture (for example, from a petroleum product), without dissolving the remaining components and not dissolving in them. Of greatest interest for purification purposes are those solvents that are capable of dissolving various substances that included in the oils at sharply differing practical dissolution temperatures [5, 6].
When cleaning the diesel fraction from aromatic hydrocarbons, N-methylpyrrolidone is used as an extractant in a mixture with an ionic liquid (a mixture of acetic and formic acids). The authors of work [7, 8] showed that when purifying a mixture of straight-run diesel fraction and catalytic cracking gas oil using N-methylpyrrolidone with an ionic liquid, the content of aromatic hydrocarbons in the purified distillate is reduced to 8.6-8.8 % (wt.).
It is currently not possible to achieve the expected indicators with existing technologies in this area. Since special processes are not economically feasible, it is advisable to conduct research on the production of diesel fuel in accordance with EURO standards using non-traditional methods, such as acoustic, mechanical, electrical, thermal, radiation, magnetic fields affect to process. The articles present the results of studies under the influence of magnetic fields [11-13].
In [14, 15], the effect of a magnetic field on a water-oil emulsion was studied. The influence of treatment on the integrity of armor shells with water and oil emulsions has been studied, various modes of magnetic treatment have been presented in terms of evaluating its effectiveness.
It should be noted that the effect of the magnetic field on the visbreaking increases the output of light-colored products by 4-8% and reduces the rate of coking in 1.2-1.3 times,
which increases the efficiency of process. The influence of the magnetic field on the process of oil refining was studied. Numerous studies show that the quality of the products obtained in the process has improved [16].
Devices operating under the action of a magnetic field can be classified into several criteria. These includes:
- methods of obtaining magnetic fields;
- performance of magnet or electromagnet by location;
- direction of the magnetic field vector on the motion of the fluid;
- the number of crossings of the magnetic field [17, 18].
In the literature there are information on the use of magnetizing devices, magnetic activators, devices of magnetic processing, etc. to create a magnetic field during magnetic processing. Electromagnets with magnetic winding and windings of different segments, as well as wire magnets are commonly used to create magnetic fields. Magnets in a constant field, of course, are easier to use and do not require an additional source of power, the magnet is easily displaced, there is no danger of an explosion in the release of flammable gases, it is economical. The disadvantages of these magnets are the impossibility of quick adjustment of magnetic field intensity, low induction during long-term operation at high temperatures, the presence of vibrations and shocks. In contrast of the stationary magnets the device with the electromagnetic field allows to regulate the intensity of the magnetic field depending on the nature of the flow and the fluidity processed [19, 20]. Studies show that the use of magnetic processing can significantly increase the efficiency of oil refining. It has been found that when a magnetic field is applied to hydrocarbon systems, the decisive factor is the magnitude of the magnetic induction, the speed at which the magnetic field intersects with the flow in the active zone (maximum induction zone). In this article, for the first time, a comparative purifycation process using N-methylpyrrolidone and its mixture with various acids is described in details.
There is extensive information in the literature on the use of N-methylpyrrolidone and its mixtures with various substances as extract-ants [1-11]. Based on a literature review, it became necessary to study the effect of various acids in a mixture of N-methylpyrrolidone in the purification process.
Extensive information about the creation of a magnetic field and devices used in the literature is given in [11-20]. We used an electromagnetic device of a special design. In this device, a magnetic field is created by passing an electric current through a copper wire wrapped around an iron case (Figure 1).
In this work, the effect of a magnetic field on the purification of polycyclic aromatic hydrocarbons from straight-run diesel fraction was carried out.
Experimental part
In order to obtain diesel fuel in accordance with international standards, the purification process was carried out under the influence of electromagnetic field using extractant N-methylpyrrolidone, and also its mixtures with acetic, phosphoric and sulfuric acid. The process is carried out in a three-neck flask with efficient mixing of the extractant with diesel dis-
tillate under the influence of a magnetic field. The mixing process takes 15 minutes. After completing the process, the phase separation takes 15 minutes.
Research results and their discussion
The amount of aromatic hydrocarbons was determined using the sulfuric acid absorption reaction (Method for determining the content of aromatic hydrocarbons by weight method GOST 6994-54) and the iodine number method (Iodine number method GOST 207082). The characteristics of the diesel distillate used in the experiment is given in Table 1.
The experiments were carried out at different values of the parameters that affect the extraction process. The best result was obtained with a 1:1 ratio of N-methylpyrrolidone, taken as extractant, with diesel fraction under normal conditions. The results of studies on the effect of ratios of N-methylpyrrolidone mixed with acids are shown in Table 2. As can be seen from table 2, the best results were obtained when using N-methylpyrrolidone with acids in a ratio of 1:1:1.
Table 1. The characteristics of the diesel distillate
№ Indicators Values
1 Density, at 200C, kg/m3 0.8450
2 Total amount of sulfur, % (wt.) 0.0895
3 Kinematic viscosity, mm2/s 6.2
4 Freezing temperature, 0C -36
5 Turbidity temperature, 0C -25
6 Flash point, 0C 72
7 Iodine number 1.83
8 Acidity 57.7
9 Aromatic hydrocarbons, % (wt.) 18.08
10 Actual resin, % (wt.) 3.4
Fractional composition, % (wt.)
Begining of boiling, 0C 222
11 50% boils , 0C 296
96% boils , 0C 357
End of boiling, 0C 367
12 Residue 3.8
Table 2. The amount of aromatic hydrocarbons after extraction in primary processing diesel distillate.
Used extractant Ratios with diesel fraction Residual content of aromatics, % (wt.)
N-methylpyrrolidone 1:1 10
N-methylpyrrolidone + Acetic acid 1:1:1 10
N-methylpyrrolidone + Sulfuric acid 1:1:1 10
N-methylpyrrolidone + Phosphoric acid 1:1:1 11
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2 T3
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16
14
12
10
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A 3
10 20 30 40 50
Magnetic field intensity, mT
60
Figure 2. Effect of magnetic field to extraction process. 1 - N-methylpyrrolidone; 2 - N-methylpyrrolidone with Acetic acid; 3 - N-methylpyrrolidone with Sulfuric acid; 4 - N-methylpyrrolidone with Phosphoric acid.
8
6
4
2
0
0
The results of the analysis showed that the content of aromatic hydrocarbons has decreased from 18.08 to 10%.
Further studies were carried out on the influence of the magnetic field on the cleaning process. The results of the experiments are given in Figure 2.
The extraction process was carried out under the influence of a magnetic field of various intensity (5-50 mT).
As can be seen from Figure 2, high results were obtained at a magnetic field intensity of 20 mT, which corresponds to the minimum content of aromatic hydrocarbons.
Thus, the optimal conditions for conducting the process are:
- temperature 200C
- pressure 760 mm Hg.
- ratio of diesel fraction to N-methylpyr-rolidone 1:1
- ratio of diesel fraction to N-methylpyrrolidone and acids 1:1:1
- magnetic field intensity 20 mT
However, under the same conditions result of extraction process under the influence of magnetic field at 20 mT further decrease in the content of aromatic hydrocarbons to 6% (wt.). Thus, the content of aromatic hydrocarbons is reduced by 67% with the use of a magnetic field, against 45% without it. The results of studies (Figure 2) on the extraction of the diesel fraction under the influence of a magnetic field with an intensity of 20 mT using N-me-thylpyrrolidone with acids (acetic, sulfuric, phosphoric) as an extractant showed that despite the reduction of aromatic hydrocarbons to 7% (wt.) not reached the required concentration.
Conclusions
- studies were carried out on the extraction purification of diesel fuel with N-methylpyrrolidone and its mixture with various acids, and it was found that, regardless of the nature of the acid used, the residual content of aromatics remained unchanged at about 10% (wt.);
- while using solely N-methylpyrrolidone as an extractant under magnetic field with an intensity of 20 mT, diesel fuel was obtained with a content of 6% (wt.) aromatic hydrocarbons, which corresponds to the EURO-5 standard;
- studies on the extraction purification of diesel fuel under the influence of a magnetic field in the case of using a mixture of N-methylpyrrolidone with different acids as an extractant showed that despite the decrease in the concentration of aromatic hydrocarbons (7% (wt.)), the required result was not achieved.
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MAQNiT SAHOSiNiN TOSiRi ALTINDA EKSTRAKSiYA ÜSULU iLE EKOLOJi TOMiZ DiZEL
YANACAGININ ALINMASI
B.G.Abdulov, O.A.Has3nov
Hazirda neft emali zavodlarinda birba§a qovulmadan alinan dizel fraksiyasinin tarkibinda politsiklik aromatik karbohidrogenlarin miqdari gox oldugundan standartlara cavab vermir. Bu problem müxtalif üsullarla hall olunur. Taqdim olunan elmi maqalada bu problem maqnit sahasinin tasiri altinda ekstraksiya prosesindan istifada etmakla hayata kegirilir. Bu maqsadla dizel fraksiyasinin ekstraksiya prosesi maqnit sahasinin tasiri altinda ham halledici kimi tamiz N-metilpirrolidondan, ham da onun sirka, sulfat, fosfor tur§ulari qari§igi ila ekstragent kimi istifada etmakla aparilmiijdir. Tadqiqat naticasinda müayyan olunmu§dur ki, ekstragent kimi tamiz halda N-metilpirrolidondan istifada etmak maqsadauygundur. Bela ki, bu zaman naticada dizel fraksiyasinin tarkibinda politsiklik aromatik karbohidrogenlarin miqdari 6 % (kütla) ta§kil edir ki, bu da AVRO-5 standartlarina cavab verir. Prosesin optimal §araiti a§agidaki kimidir:
- temperatur 200C;
- tazyiq 760 mm civa st.;
- nisbat 1:1 (Dizel : N-metilpirolidon);
- qariijdiricinin sürati - 70 dövr/daq;
- maqnit sahasinin intensivliyi - 20 mT;
Agar sözlar: dizel, ekstraksiya üsulu, maqnit sahasi, N-metilpirrolidon.
ПОЛУЧЕНИЕ ЭКОЛОГИЧЕСКИ ЧИСТОГО ДИЗЕЛЬНОГО ТОПЛИВА МЕТОДОМ ЭКСТРАКЦИИ
ПОД ВОЗДЕЙСТВИЕМ МАГНИТНОГО ПОЛЯ
Б.Г.Абдулов, А.А.Гасанов
В настоящее время полициклические ароматические углеводороды во фракции дизельного топлива, получаемой прямой перерагонкой нефти, не соответствуют нормативам. Эта проблема решается по-разному. В представленной научной статье эта задача реализована с помощью процесса экстракции под действием магнитного поля. Для этого процесс экстракции дизельной фракции проводили под действием магнитного поля, используя в качестве экстрагента чистый ^метилпирролидон и его смесь уксусной, сульфатной и фосфорной кислот. В результате исследований установлено, что в качестве экстрагента целесообразно использовать чистый ^метилпирролидон. Так, в этом случае количество полициклических ароматических углеводородов в дизельной фракции составляет 6% (масс), что соответствует нормам ЕВРО-5. Оптимальные условия процесса следующие:
- температура 200С;
- давление 760 мм рт.ст.;
- соотношение 1:1 (Дизель : ^метилпирролидон);
- скорость мешалки - 70 об/мин;
- интенсивность магнитного поля - 20 мТл;
Ключевые слова: дизель, метод экстракции, магнитное поле, Nметилпирролидон.
