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CHEMICAL PROBLEMS 2022 no. 3 (20) ISSN 2221-8688
229
UDC 665.64 665.35
STUDY OF THE PROCESS OF OBTAINING ALTERNATIVE MOTOR FUELS USING
VEGETABLE OILS
I.A. Khalafova, N.K. Andryushenko
Azerbaijan State University of Oil and Industry Azadliq Ave., 34, Baku, AZ1010, Azerbaijan Republic e-mail: [email protected]
Received 06.05.2022 Accepted 10.07.2022
Abstract: The growing shortage of oil resources makes it necessary to find alternative energy sources. The leading place among them today belongs to biofuels, both due to sufficient and affordable resources, and relatively advanced technologies for their production. The requirements of modern standards for the quality of the resulting gasolines limit the content of aromatic hydrocarbons in them to no more than 42% by mass. (Euro-3), and 35% of the mass. (Euro-4 and Euro-5). Therefore, studies on the involvement of vegetable raw materials in the processes of obtaining gasoline fractions are aimed either at obtaining highly aromatic gasoline with its subsequent compounding, or at searching for catalytic systems that make it possible, if any, to reduce the content of aromatic hydrocarbons in the composition of the resulting gasolines during joint cracking of the mixture of oil and vegetable raw materials. In this work, using the model oleic acid as an example, the mechanism of the conversion of fatty acids of vegetable oils during their catalytic conversion into hydrocarbons of the gasoline series was studied. The process was studied using a mixture of vacuum gas oil with vegetable oils as cracking catalysts, industrial cracking catalysts Omnikat-210P and Tseokar-600 in pure form and in their mixture with natural halloysite nanotubes. Halloysites belong to the family of kaolinite clay minerals with a high Al/Si ratio as compared to other aluminosilicates and have a predominantly hollow tubular structure and consist of layers of aluminum and silicon oxides that are rolled into tubes. The process of catalytic cracking of vacuum gas oil with the involvement of vegetable oils (waste vegetable oils taken from the Chudo-Pechka chain of stores) in the amount of 5 wt % was studied. Keywords: oleic acid, vegetable oils, catalytic cracking, halloysites, reaction mechanism, catalyst, Omnikat-210P, Tseokar-600
DOI: 10.3273 7/2221-8688-2022-3-229-241
Introduction
The ever-growing shortage of oil resources makes it necessary to search for alternative energy sources, among which today the leading place belongs to biofuels, both due to sufficient and affordable resources, and relatively advanced technologies for their production.
The leading trend in obtaining second-generation biofuels is the creation of a technology for the large-scale production of high-quality motor fuels from oxygen-containing raw materials of plant origin, using the existing fuel transport system and the infrastructure of oil refineries. The basis of these processes is both the hydro-treatment of
mixed feedstock (vegetable oils and fats and diesel oil fraction at hydro-treatment and hydro-cracking units ("Green Diesel"), and the joint cracking of a mixture of gas oil fractions with vegetable feedstock in order to obtain a gasoline fraction and/or olefins ("Green Gasoline", "Green Olefin") [1-5].
The analysis of literary sources made it possible to single out the main class of catalysts used in the production of gasoline during catalytic cracking of a mixture of petroleum fractions and vegetable raw materials. Basically, these are synthetic zeolite-containing catalysts with strong acid centers and various porosities. The most widely studied in the processes of
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CHEMICAL PROBLEMS 2022 no. 3 (20)
joint processing of vegetable oils, as well as their mixtures with petroleum fractions, is the catalyst HZSM-5, HZSM-10, HZSM-12 (the so-called 5-12-ring zeolites) [6, 7].
However, it should be noted that gasolines obtained during the process of catalytic cracking of vegetable oils have a high content of aromatic hydrocarbons. This can be explained as being due to the high content of unsaturated fatty acids with one, two or three double bonds in the triglyceride molecule of vegetable oils which, under the effect of high temperatures, are converted into olefin fragments and subsequently lead to the formation of aromatic hydrocarbons.
The requirements of modern standards for the quality of the resulting gasolines limit the content of aromatic hydrocarbons in them to no more than 42% by mass. (Euro-3), and 35% of the mass. (Euro-4 and Euro-5). Therefore, studies on the involvement of vegetable raw materials in the processes of obtaining gasoline
fractions are aimed either at obtaining highly aromatic gasoline with its subsequent compounding, or at searching for catalytic systems that make it possible, if any, to reduce the content of aromatic hydrocarbons in the composition of the resulting gasolines during joint cracking of the mixture of oil and vegetable raw materials.
The purpose of this work is to study the possibility of involving vegetable oils obtained from oil-containing crops growing on the territory of Azerbaijan in the process of obtaining gasoline fractions by processing a mixture of various petroleum fractions with these vegetable oils. In the work, a mixture of waste vegetable oils taken from the Miracle Pechka chain of stores was used as oil. At the moment, the process of recycling waste vegetable oils has not been established. Exploring the possibility of using used oils in the production of motor fuels, we can talk about improving the environment.
Experimental part
In this work, industrial cracking catalysts Omnikat-210P and Tseokar-600 in pure form and in a mixture of natural halloysite nanotubes
were studied as catalysts for cracking a mixture of vacuum gas oil with vegetable oils (Table 12).
Table 1. Quality indicators of the cracking catalyst Omnikat-210P with a promoter for afterburning
CO into CO2 by «Grace»
Name of indicators average minimal maximum
Microactivity, min. (ASTM (DEVISON) after heat treatment at 760 °C, 5 h, 1.35 bar 100% steam 75 73
Physical properties after calcination at 540°C, 3 h
- surface area, m2/g 200 180 220
- pore volume, mm2/g 0.4 0.35 0.43
- bulk density, g/ml 0.65 0.61 -
- wear resistance (Davison index) 5 - 8
particle size distribution, % wt.
0-20 microns 1 - 2
0-40 microns 15 10 20
0-80 microns 60 90 70
0-149 microns 92 90 100
average particle size, microns 70 65 78
Chemical composition, % wt.
- Al oxide (Al2O3), % wt. 44.0 41.0 47.0
- oxide Na (Na2O), % wt. 0.25 - 0.35
- oxides of rare earth elements (Re2O3), % wt. 1.9 1.6 2.2
- platinum content in the catalyst__not lower than 2 ppm
The catalyst Tseokar-600 was produced by LLC Company KATAKHIM, Russia.
Table 2. Qualitative indicators of the catalyst Tseokar-600
Name of indicator Normalized values
Bulk density under test conditions, kg/m3, within 680-780
Mass fraction of target fraction 3.0-6.0 mm, %, not less than 92
Mass fraction of whole and mechanically strong balls of fraction 2.55.0 mm, %, not less 86
Stable activity in terms of gasoline yield, %, not less than 52
Selectivity, %, not less 75
Mass fraction of moisture removed at 800 °C, %, no more 2.5
Mass fraction of rare earth elements in terms of their oxides, %, not less than 1.8
Mass fraction of components, %, not more than:
sodium oxide iron oxide 0.55 0.3
Characteristics of platinum content - volumetric ratio of carbon monoxide (IV) to carbon monoxide (II) (C02/C0), not less than 1.5
Catalyst strength under shock-abrasive action 300 s, %, not less 50
Halloysite belongs to the family of kaolinite clay minerals with a high Al/Si ratio as compared to other aluminosilicates and have a
predominantly hollow tubular structure. Content of various elements in samples of halloysites are presented in Table 3.
Table 3. Content of various elements in samples of halloysites
Content of elements, mg/kg Halloysite sam ples
USA (1) USA (2) New Zealand
1 2 3 4
S 38720 - -
K 16985 - -
Ca 20111 2406 -
Ti 1150 487 653
Cr - 50 59
Mn 562 79 43
Fe 16416 5893 3319
Co - - -
Ni - 315 -
Cu - - -
Zn 412 138 -
As 111 - -
Rb - 21 -
Sr 3084 240 19
Zr 60 63 183
Mo - 63 -
Pt - - 463
Ba 410 132 -
Pb 107 - 84
Halloysites consist of layers of aluminum and silicon oxydes, which are twisted into tubes. The silica layer is on the outer surface of the tube, while the alumina layer refers to the inner surface of the lumen (hole) [8-10]. The outer diameters of the tubes vary from 40 to 100 nm with an average value of 70 nm [9, 11]. The diameters of the inner lumen (hole) range from 10 to 50 nm and average 20 nm [13]. The tube lengths range from 0.5 to 2.0 p,m [8].
The different chemical structure of the outer and inner sides of the halloysite layer adds unique properties to halloysite nanotubes that do not exist in other nanotubes. One of the features of halloysite is the different surface and chemical properties on the inner and outer sides of the tubes [12]. Aluminum and silicon oxides
have different dielectric and ionization properties. These tubes can be selectively modified on the outside or inside, which can be useful in hydrocarbon cracking.
Halloysite nanotubes have a high specific surface area ranging from 80 to 150 m2/g due to which these minerals have a very high cation exchange capacity from 0.02 to 0.68 mol/kg [9]. Hydrated halloysite nanotubes can adsorb low molecular weight substances into the interlayer space [9, 13, 14]. The absorption of macromolecular substances with a molecular weight above 300 g/mol mainly takes place through loading into the inner lumen of tubes, which is of particular interest in the processing of heavy hydrocarbons [8, 15-16].
Fig. 1. Technological scheme of a flow unit for carrying out the process of catalytic cracking of linoleic acid. Lines: I - raw material supply line; II - gas supply line (nitrogen, air); III - collection line for liquid products; IV - collection line for gaseous products. 1 - container for raw materials; 2 -pump; 3 - reactor; 4 - condenser-refrigerator; 5 - degasser; 6 - gas clock; 7 - receiver of liquid products; 8, 9 - dehumidifier of incoming gases; B1, B2, B3 - throttle valves, 10 - gas meter, 11 -
heating furnace
The presence of acidic segments in halloysite nanoparticles due to the high content of aluminum oxide leads to the cracking of hydrocarbons. These acidic sites catalyze the heterolytic cleavage of chemical bonds which leads to the formation of unstable carbocations which undergo chain rearrangements and cleavage of C-C bonds through P-elimination or hydride ion transfer. All these processes contribute to the formation of highly reactive radicals and ions which further accelerate the cracking process [17].
The study of the mechanism of the conversion of fatty acids of vegetable oils during their catalytic conversion into hydrocarbons of the gasoline series was carried out using the example of model oleic acid. The
process of catalytic cracking of oleic acid was carried out on a flow-through laboratory unit at temperatures of 490-510 °C, WHSV 1-20 h-1 (Fig. 1).
The study of the composition of products from the process of catalytic cracking of oleic acid on the Omnikat-210P catalyst showed that as the contact time of the feedstock with the catalyst increases, the products of oleic acid conversion mainly containing aromatic compounds with no n-paraffin compounds, the content of olefinic and naphthenic hydrocarbons makes up 0.71 and 0.62% mass. respectively. As WHSV increases to 10 h-1, n-paraffins appear in the composition of the catalyzate, and the content of olefinic and naphthenic hydrocarbons increases as well (Table 4).
Table 4. Hydrocarbon Composition of Oleic Acid Cracking Products Using Omnikat-210P, Tseokar-600 Catalysts and Their Mixtures with Halloysites
Hydrocarbon composition of products, % wt. Catalysts
Omnikat-210P Omnikat-210P + halloysite Zeokar-600 Zeokar-600 + halloysite
WHSV = 1 h-1
paraffins 0 0 0 0
olefins 0.71 2.12 0 0.12
cycloparaffin 0.62 0.85 0 0.15
aromatic, incl. 94.37 90.71 94.68 93.68
benzene 4.15 3.90 10.95 8.65
alkylbenzenes 25.95 32.33 19.35 27.11
Bicyclic (naphthalene and its derivatives) 36.8 31.20 35.63 32.10
Tricyclic (phenanthrenes, anthracenes) 13.46 11.82 14.75 12.82
Tetracyclic (pyrene chrysene and their derivatives) 14.01 11.46 14.0 13.0
WHSV = 10 h-1
paraffins 1.65 1.95 1.38 1.52
olefins 2.14 2.46 3.12 3.68
Cycloparaffins (ethyl-cyclohexane) 1.35 1.94 0.34 0.95
aromatic, incl. 91.54 88.33 89.84 88.53
benzene 3.18 2.75 7.65 5.98
alkyl benzenes 30.24 34.65 26.26 30.14
Bicyclic (naphthalene and its derivatives) 31.12 30.80 34.12 31.20
Tricyclic (phenanthrenes, anthracenes) 12.00 10.46 12.45 10.34
Tetracyclic (pyrene, chrysene and their derivatives) 13.00 9.67 12.36 10.87
WHSV = 20 h-1
paraffins 14.60 12.2 11.5 10.2
olefins 22.10 24.3 20.34 22.6
cycloparaffins 6.40 8.3 4.6 5.3
aromatic, incl. 56.57 55.0 62.86 61.15
benzene 2.85 1.85 3.83 3.00
alkyl benzenes 42.30 45.95 34.43 39.55
polycyclic aromatics 11.42 7.2 24.6 18.6
Benzoic acid 0.18 0.12 0.43 0.35
Linoleic acid 0.05 0.06 0.07 0.02
A decrease in the contact time of the raw material with the catalyst also affects the composition of the resulting aromatic compounds. The content of benzene decreases to 3.18% mass, while the total content of various benzene derivatives slightly increases -30.24% mass. An increase in WHSV also leads to a decrease in polynuclear aromatic compounds.
The data obtained allow us to suggest a mechanism for the formation of aromatic compounds along two routes: the cyclization of the hydrocarbon chain, predominantly with the participation of the hydrogen atom bonded to the C atom in the a-position with respect to the carbonyl group, which usually exhibits high
An increase in WHSV to 20 h-1 in the composition of the obtained catalyzate significantly increases the amount of paraffin, olefin and cycloparfin compounds. The content of aromatic compounds decreases to 56.57% mass, while with WHSV 1-10 h-1 it is 94.3791.54% mass. The composition of aromatic compounds is represented mainly by alkylbenzenes (Table 5).
activity, as well as the interaction of olefinic hydrocarbons formed when C-C bonds are cleaved predominantly in the P-position with respect to the double bond of fatty acid molecules (according to the Diels-Alder reaction) (Fig. 2-3)
Table 5. The composition of alkyl benzenes formed during the cracking of oleic acid
Composition of alkyl benzenes, % mass. Catalyst
0mnikat-210P 0mnikat-210P + halloysite
WH [SV, h-1
1 10 20 1 10 20
Methyl-benzene 1.8 2.01 2.55 1.3 1.50 2.81
1,2 dimethylbenzene 2.27 3.14 6.64 6.26 8.82 14.68
1,3 dimethylbenzene 1.05 1.12 2.62 1.35 1.54 3.72
1,2,3-trimethylbenzene 0.30 0.55 3.05 2.55 2.7 3.02
1,2-diethylbenzene 6.16 7.66 9.16 7.32 7.65 8.20
1-ethyl-2-methyl benzene 3.06 4.68 6.18 4.85 4.41 5.37
1-methyl-3-propyl benzene 5.95 5.83 8.30 4.65 4.95 5.47
1 -methyl-2-(2-propenyl)benzene 5.36 5.25 3.8 4.05 3.08 2.68
Total: 25.95 30.24 42.3 32.33 34.65 45.95
Fig. 2. Scheme of formation of aromatic compounds during the splitting of oleic acid by the
Diels-Alder reaction.
Fig. 3. Scheme of the formation of aromatic compounds during the splitting of oleic acid by the
cyclization reaction
This suggests that aromatization of oxygenates can occur before deoxygenation and this is favored by the presence of a carbonyl group [18].
After ring closure, the carbonyl group can be converted at the acid sites of the catalyst during tautometry to the enol form, which, in turn, can be dehydrated and further
dehydrogenated to form o-xylene, or after ring closure, decarboxylation and dehydrogenation can occur to form the corresponding alkyl-benzenes.
Reducing the contact time of the feedstock with the catalyst leads to the decrease in the share of cleavage reactions of long-chain carbon chains and to the decrease in the share of
formed benzene and an appropriate increase in the share of alkyl-benzenes. This fact is also confirmed when a mixture of Omnikat-210P with halloysites is used as a catalyst.
Studies showed that in the case of using catalytic systems with halloysites, the mechanism of formation of aromatic compounds proceeds mainly along the first route.
Table 1 shows that the addition of halloysites to the composition of catalysts leads to an increase in the amount of olefinic hydrocarbons formed while reducing the amount of benzene formed.
The amount of o-xylene formed when using a mixture of the 0mnikat-210P catalyst with halloysites is higher even at WHSV = 1 h-1 and amounts to 6.26 % mass, while when using the 0mnikat-210P catalyst with halloysite at WHSV = 20 h-1 content of o-xylene increases to 14.68%.
The use of Tseocar-600 as a catalyst at low mass feed rates (1 h-1) leads to almost 100% conversion of oleic acid into aromatic compounds. The composition of the catalyzate does not contain paraffin, olefin or cycloparfin compounds.
The content of the resulting alkyl benzenes is lower, and the content of polycyclic aromatic compounds is somewhat higher than when using the 0mnikat-210P catalyst and its mixture with halloysites.
When halloysites are added to the
composition of the tested catalyst at WHSV= 1 h-1, the amount of alkyl-benzenes formed noticeably increases, while the amount of polycyclic aromatic compounds formed decreases.
The use of a mixture of Tseocar-600/halloysite leads to a decrease in the composition of the formed aromatic compounds of benzene.
When using Tseokar-600 in its pure form and with halloysite at WHSV = 20 h-1, the amount of n-parafins and olefins increases, and the composition of hydrocarbon gases is mainly represented by unsaturated compounds (ethylene, propylene).
The use of catalysts 0mnikat-210P and 0mnikat-210P/halloysite leads to a noticeable decrease in the composition of the formed gases of ethylene cracking, with a simultaneous increase in the amount of propylene formed.
At the next stage of the research, the process of catalytic cracking of vacuum gas oil with the involvement of vegetable oils (cottonseed, sunflower, as well as a mixture of vegetable oils used in the food industry) in its composition amounting to 5% mass., was considered which was carried out on flow laboratory installation in the temperature range of 480-520 °C and WHSV = 22.0 h-1. V
The material balance of the process of catalytic cracking of the 5% mixture of waste vegetable oils with vacuum gas oil is given in table 6.
Table 6. Material balance of the process of catalytic cracking of a 5% mixture of used vegetable oils with vacuum gas oil at a temperature of 480-520 °C
Type of raw material Catalyst
Omnikat-210P 0mnikat-210P + halloysite Tseokar-600 Tseokar-600+ halloysite
Температура процесса, оС
480 500 520 480 500 520 480 500 520 480 500 520
Taken, % mass.:
Vacuum gas oil 95 95 95 95 95 95 95 95 95 95 95 95
Vegetable oil 5 5 5 5 5 5 5 5 5 5 5 5
Received, % mass.:
Gases up to C4 13.0 14.5 18.6 13.5 15.0 19.5 13.5 15.7 19.2 14.4 16.8 20.1
Gasoline fraction n.k.-200 °C 38.8 46.3 41.6 40.0 47.5 42.6 39.8 46.8 44.4 40.8 49.4 45.1
Light gas oil 200350 °C 16.2 6.3 4.8 15.5 6.3 4.1 17.5 7.0 4.5 18.6 6.8 4.0
heavy gas oil 26.9 27.4 29.0 25.8 25.9 28.2 24.1 25.3 25.9 21.2 21.8 25.0
coke 2.7 2.9 3.4 2.6 2.8 3.2 2.8 3.0 3.5 2.6 2.7 3.3
Losses + water* 2.4 2.6 2.6 2.6 2.5 2.4 2.3 2.2 2.5 2.4 2.5 2.5
Conversion, % mass. 54.5 63.7 63.6 56.1 65.3 65.3 56.1 65.5 67.1 57.8 68.9 68.5
Selectivity for gasoline, % 71.2 73.0 65.4 71.3 73.0 65.2 71.0 71.5 66.2 71.0 72.0 66.0
Results and discussion
An analysis of the data obtained makes it possible to conclude that there is a tendency to raise the yield of the gasoline fraction with rise in temperature of the catalytic cracking process from 480 °C to 500 °C. Under these conditions, an increase in the yield of gas and gasoline fractions and a decrease in the content of heavy gas oil were revealed. At the same time, an increase in the yield of gasoline fraction at a temperature of 500 °C in comparison with the data obtained during the processing of pure
vacuum gas oil is 0.7-1.4%, and the largest increase is observed for catalytic systems with halloysites (Fig. 4).
The smallest rise in the gasoline fraction is observed when using a mixture of used vegetable oils (having a heavier composition) for Omnikat-210P and Tseokar-600 catalysts (0.7-0.8% mass.). However, the addition of halloysites to the composition of the catalyst makes it possible to slightly increase the yield of gasoline (up to 1% mass.).
Fig. 4. Increase in the yield of gasoline fraction for a 5% mixture of vegetable oils with vacuum gas oil in comparison with the processing of pure v/gas oil at 500 °C
Table 7 provides the quality indicators of gasoline fractions obtained in the process of catalytic cracking of a mixture of vacuum gas oil with used vegetable oils at 500 °C in
comparison with traditional catalytic cracking gasolines, received on H. Aliyev Oil Refinery [19].
Table 7. Physical and chemical properties of gasolines from the process of catalytic cracking of vacuum gas oil with waste vegetable oils using catalysts Omnikat-210P (I), Tseokar-600 (II) and
their mixtures with halloysites (IA, IIA)
Indicators Catalytic cracking gasoline (H.Aliyev Oil Refinery) Catalyst
(I) (IA) (II) (II A)
Vacuum gas oil + vegeta >% mixture of used ble oils
1 2 3 4 5 6
Density at 20 °C, kg/m3 726.2-738.9 739.0 738.2 737.0 736.4
Fractional composition, °C:
start of boiling 35-38 37.0 37.0 37.0 35.0
10% is distilled at the same rate 50-70 68.0 60.0 55.0 50.0
50 % — 104-115 115.0 112.0 106.0 105.0
90 % — 185-190 190.0 190.0 185.0 183.0
End of boiling 195-205 205.0 202.0 200.0 200.0
Iodine number I2/g 30-50 40.2 44.0 45.1 49.0
Acidity mg KOH/ 100 cm3 0.30-1.50 0.99 0.93 0.95 1.07
Saturated vapor pressure, kPa 38.6-54.2 43.1 45.0 46.1 47.4
Concentration of actual resins, mg/100 cm3 0.95-2.1 1.60 1.52 1.54 1.47
Sulfur content, % mass. 0.012-0.016 0.011 0.011 0.011 0.011
Copper plate test + + + + +
Hydrocarbon composition, % mass.:
n-paraffins 15.0-30.0 21.45 18.93 17.34 14.4
iso-paraffins 20.0-30.0 24.30 25.40 24.7 27.6
naphthenes 7.0-16.0 6.30 7.65 7.12 7.65
Olefins 15.0-18.0 17.90 19.42 19.54 20.85
aromatics, incl. 23.0-30.0 30.05 28.60 31.30 29.50
benzene 1.8-3.2 1.85 1.34 2.05 1.65
Octane number 90-91 91 91 91.5 91.5
Gasoline fractions obtained in the process of catalytic cracking of mixtures of vacuum gas oil with waste vegetable oils were studied in the laboratory of H.Aliyev Oil Refinery (Table 7). The group hydrocarbon composition of gasoline fractions was analyzed chromatographically on a Perkin Elmer Auto System XL chromatograph (column length 100 m, diameter 250 p,m, filler dimethylsiloxane).
As can be seen from Table 7, the quality indicators of gasoline fractions obtained in the process of catalytic cracking of a mixture of vacuum gas oil with waste vegetable oils are almost identical to the quality indicators of traditional catalytic cracking gasolines.
However, they have a slightly heavier fractional and more flavored hydrocarbon composition.
Thus, in the course of the current study, the possibility of involving vegetable oils in the process of catalytic cracking was revealed. It found that by adding 5% vegetable oils to the composition of vacuum gas oil, the yield of gasoline fraction rises with a simultaneous improvement in the quality of the resulting gasoline, both operational and environmental. At the same time, the addition of halloysites to the composition of industrial catalytic cracking catalysts makes it possible to reduce the content of aromatic hydrocarbons in the composition of the gasoline fraction by 1.4-1.8 mass%.
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BÍTKÍ YAGLARINDAN ÍSTÍFAD9 EDÍL9N ALTERNATÍV MÜH9RRÍK YANACAQLARININ ALINMASI PROSESÍNÍN ARA§DIRILMASI
i.A. Xalafova, N.K. Andryu^enko
Azdrbaycan Dövldt Neft vd Sdnaye Universiteti Azadliq pr., 34, Baki, AZ1010, Azdrbaycan Respublikasi e-mail: [email protected]
Xülasa: Neft ehtiyatlannm artan 9ati§mazligi alternativ enerji manbalarinin tapilmasinin tacili ehtiyacini dikta edir. Bu gün onlarin arasinda aparici yer ham kifayat qadar va alveri§li resurslara, ham da onlarin istehsali ü9ün nisbatan qabaqcil texnologiyalara göra bioyanacaqlara maxsusdur. Benzinlarin keyfiyyatina dair müasir standartlarin talablari onlarin tarkibindaki aromatik karbohidrogenlarin kütlasini 42%-dan (Avro-3) va 35%-dan (Avro-4 va Avro-5) 9ox olmamaqla mahdudla§dirir. Buna göra da, bitki xammalinin benzin fraksiyalarinin alinmasi proseslarina calb edilmasina dair tadqiqatlar ya sonraki birla§ma ila yüksak aromatik benzin alda etmaya, ya da mümkünsa aromatik tarkibini azaltmaga imkan veran katalitik sistemlarin axtari§ina yönaldilmi§dir. Bu i§da olein tur§usu modelindan nümuna kimi istifada edilmakla, bitki yaglarinin yag tur§ularinin benzin sirasinin karbohidrogenlarina katalitik 9evrilmasi zamani onlarin 9evrilma mexanizmi tadqiq edilmi§dir. Sanaye krekinq katalizatorlarindan Omnikat-210P va Tseokar-600-dan tamiz formada va onlarin tabii halloysit nanoborucuqlari ila qari§igindan istifada etmakla vakuum qazoylunun bitki yaglari ila qari§iginin krekinq prosesi tadqiq edilmi§dir. Bitki man§ali yaglarin (£udo-Pe9ka magazalar §abakasindan götürülmü§ tullanti bitki yaglari) 5 küt. % hacminda calb edilmasi ila vakuum qazoylunun katalitik krekinq prosesi tadqiq edilmi§dir.
A?ar sözlar: olein tur§usu, bitki yaglari, katalitik krekinq, halloysitlar, reaksiya mexanizmi, katalizator, Omnikat-210P, Tseokar-600
ИССЛЕДОВАНИЕ ПРОЦЕССА ПОЛУЧЕНИЯ АЛЬТЕРНАТИВНЫХ МОТОРНЫХ ТОПЛИВ С ИСПОЛЬЗОВАНИЕМ РАСТИТЕЛЬНЫХ МАСЕЛ
И.А. Халафова, Н.К. Андрюшенко
Азербайджанский Государственный Университет Нефти и Промышленности Пр. Азадлыг 34, Баку, AZ1010, Республика Азербайджан эл. адрес: khalafova. [email protected]
Аннотация: Возрастающий дефицит нефтяных ресурсов диктует настоятельную необходимость поиска альтернативных энергоисточников. Ведущее место среди них на сегодняшний день принадлежит биотопливам, благодаря достаточным и доступным ресурсам и относительно развитым технологиям их получения. Требования современных стандартов к качеству получаемых бензинов ограничивают содержание ароматических углеводородов в них не более 42 % масс. (Евро-3), и 35 % масс. (Евро-4 и Евро-5). Поэтому исследования по вовлечению растительных видов сырья в процессы получения бензиновых фракций направлены либо на получение высокоароматизированного бензина с последующим его компаундированием, либо на поиск каталитических систем, позволяющих, по возможности, снизить содержание ароматических углеводородов в составе получаемых бензинов при совместном крекинге смеси нефтяного и растительного сырья. В данной работе на примере олеиновой кислоты изучен механизм превращения жирных кислот растительных масел при каталитическом превращении их в углеводороды бензинового ряда. Процесс исследован при использовании в качестве катализаторов крекинга смеси вакуумного газойля
с растительными маслами промышленных катализаторов крекинга Омникат-210П и Цеокар-600 в чистом виде и в смеси их с природными нанотрубками галлуазитов. Галлуазиты принадлежат к семье каолинитовых глинистых минералов с высоким соотношением Al/Si по сравнению с другими алюмосиликатами и имеют преимущественно полую трубчатую структуру и состоят из слоёв оксидов алюминия и кремния, которые скручены в трубки. Исследован процесс каталитического крекинга вакуумного газойля с вовлечением в его состав растительных масел (отработанных растительных масел, взятых из сети магазинов «Чудо-печка») в количестве 5 % масс.
Ключевые слова: олеиновая кислота, растительные масла, каталитический крекинг, галлуазиты, механизм реакции, катализатор, Омникат-210П, Цеокар-600
